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Accepted Article
Accepted Article
Title: Construction of a Diverse Range of Boron Heterocycles via Ring
Expansion of a Carboranyl-Substituted 9-Borafluorene
Authors: Tobias Bischof, Lukas Beßler, Ivo Krummenacher, Leon

Erhard, Holger Braunschweig, and Maik Finze
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To be cited as: Chem. Eur. J. 2023, e202300210
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01/2020
Chemistry - A European Journal 10.1002/chem.202300210
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RESEARCH ARTICLE
Construction of a Diverse Range of Boron Heterocycles via Ring
Expansion of a Carboranyl-Substituted 9-Borafluorene
Tobias Bischof,[a,b] Lukas Beßler,[a,b] Ivo Krummenacher,[a,b] Leon Erhard,[a,b] Holger Braunschweig,*[a,b]
and Maik Finze*[a,b]
[a] Dr. T. Bischof, L. Beßler, Dr. I. Krummenacher, L. Erhard, Prof. Dr. H. Braunschweig, Prof. Dr. M. Finze
Accepted Manuscript
Institute for Inorganic Chemistry
Julius-Maximilians-Universität Würzburg
Am Hubland, 97074 Würzburg, Germany
E-mail: h.braunschweig@uni-wuerzburg.de, maik.finze@uni-wuerzburg.de
[b] Dr. T. Bischof, L. Beßler, Dr. I. Krummenacher, L. Erhard, Prof. Dr. H. Braunschweig, Prof. Dr. M. Finze
Institute for Sustainable Chemistry & Catalysis with Boron (ICB)
Julius-Maximilians-Universität Würzburg
Am Hubland, 97074 Würzburg, Germany
Supporting information for this article is given via a link at the end of the document.
Abstract: Direct insertion of unsaturated substrates into a five- have aroused great interest for applications as pharmaceutical
membered borole ring is a useful method to obtain valuable drugs or active components in optoelectronic devices.[5-7]
heterocycles containing one or more three-coordinate boron atoms. A We and others have demonstrated that insertion reactions to
highly Lewis acidic 9-o-carboranyl-9-borafluorene, in which the o- give ring-expanded products are facilitated by a more electrophilic
carboranyl substituent is connected via one of the cluster carbon and Lewis acidic boron center, favoring initial adduct formation of
atoms to the boron atom of the 9-borafluorene unit, was found to react the nucleophilic substrates with the Lewis acidic boron center.[8,9]
with a vast array of unsaturated molecules, such as alkynes, Our recently reported 9-o-carboranyl-9-borafluorene 1, in which
aldehydes and various organic azides, to form larger boraheterocyclic the boron atom is rendered highly Lewis acidic and electrophilic
products. The ring expansion reactions of the central borole ring by the electron-withdrawing 1,2-dicarba-closo-dodecaboranyl
proceed rapidly at room temperature, cementing the role of the o- substituent, allowed the insertion of even weakly nucleophilic
carboranyl substituent in enhancing the insertion reactivity of 9- substrates such as alkenes at room temperature, showing that its
borafluorenes. central borole ring is strongly activated toward B−C insertion and
subsequent ring expansion (Figure 1).[9]
In this article we expand on the reactivity of the 9-borafluorene 1
by examining its insertion chemistry with a wide range of other
Introduction unsaturated organic molecules. We found that it was highly
reactive, generating a library of new boraheterocycles by ring
Since the isolation of the first monocyclic borole by Eisch and expansion under very mild conditions, almost exclusively at room
coworkers in 1969,[1] pentaphenylborole and other members of its temperature. Also reported is an unprecedented insertion of an
class continue to be a subject of considerable interest.[2] Due to iminoborane, leading to a BN analogue of a borepin.
their antiaromaticity and the presence of a Lewis acidic boron
center, boroles offer numerous opportunities to probe new
chemical and physical properties.
One of the essential characteristics of boroles is their chemical
versatility. Even slight modifications in the ring substituents can
lead to substantial changes in intrinsic properties, such as their
stability. For instance, dibenzannulated borole derivatives, also
referred to as 9-borafluorenes,[2e] are more stable than many
monocyclic borole derivatives.[3] Despite their lower associated
Figure 1. Structure of 9-borafluorene 1 and 6,7-dihydroborepin products from
antiaromaticity and reactivity, they still exhibit the typical behavior the insertion of terminal alkenes (R1 = alkyl or aryl).[9] Unlabeled vertices of the
of boroles towards nucleophiles, including the formation of Lewis 1,2-dicarba-closo-dodecaborane are BH units.
base adducts and insertion reactions.[2e] Through simple addition
of unsaturated substrates such as organic azides or alkynes, the
latter reactions provide access to a variety of ring-expanded boron Results and Discussion
heterocycles.[2e,4] Among the different classes of compounds that
can be obtained in this way, six-membered 1,2-azaborinines and A variety of organic substrates, including alkynes, organic azides
seven-membered borepins are more prominent examples that and carbodiimides, were reacted with the Lewis acidic 9-o-
1
This article is protected by copyright. All rights reserved.
RESEARCH ARTICLE
carboranyl-9-borafluorene 1 to give a diverse range of ring-
expanded six-, seven-, and eight-membered boracycles, as
shown in Scheme 1. The discussion of the results is organized
below by the type of element inserted into the borole ring, starting
with carbon and moving through nitrogen to the heteroatoms
phosphorus and oxygen. The properties of the resulting boron
heterocycles will not be discussed in detail, since the heterocyclic
cores of these molecules have literature precedence.
Accepted Manuscript
Figure 2. Synthesis and molecular structures of borepins 2a and 2b. Thermal
ellipsoids are set at 50% probability and hydrogen atoms have been omitted
for clarity.
By using a diyne, we intended to install a peripheral alkyne

unit on the borepin that would be available for further
functionalization. However, the reaction of 1 with 1,5-hexadiyne
resulted in insertion of both alkyne units (into separate borole
units), giving ethylene-bridged bis(borepin) 2c as the product
(Figure 3). Attempts to prevent a second insertion of the diyne
were unsuccessful, suggesting that the reaction of the alkynyl-
substituted borepin intermediate with another equivalent of 1 is
faster than the first insertion. The structure of bis(borepin) 2c was
elucidated by X-ray diffraction and multinuclear NMR
spectroscopy. The latter analysis revealed that 2c is present as a
Scheme 1. Overview of boraheterocyclic scaffolds prepared herein from ring 7:3 ratio of diastereomers in solution, which are likely formed by
expansion of 9-borafluorene 1 with unsaturated organic substrates (R1 = 2-Me-
closo-1,2-C2B10H10; R2 and R3 = see text). restricted rotation about the B−C single bond joining the
carborane and the borepin units. Alternatively, planar chirality
Carbon insertions. We have previously shown that 9- associated with the configurationally stable puckered borepin
borafluorene 1 efficiently undergoes insertion reactions with rings could lead to the formation of diastereomers.[25]
alkenes to give dibenzannulated 6,7-dihydroborepins (Figure 1).[9]
We therefore expected similar reactivity from the more
nucleophilic alkyne substrates, whose reactions with various
monocyclic and annulated borole derivatives are already well
studied.[10]
As predicted, reactions of 1 with phenyl- and
diphenylacetylene resulted in the formation of the corresponding
seven-membered dibenzoborepins 2a and 2b, respectively
(Figure 2). Although the reactions are quantitative by NMR
spectroscopy within minutes at room temperature, isolation of the
products in pure form was associated with significant yield losses.
Dibenzoborepins 2a and 2b were obtained in 33% and 62% yields,
respectively. The low isolated yields are mainly due to the multiple
washing steps required to remove traces (up to a few percent) of
the free carborane cluster. Besides multinuclear NMR
spectroscopy, the products were further characterized by single-
crystal X-ray diffraction, revealing their non-planar twist-boat
structure (Figure 2). The spectroscopic and structural data (listed
Figure 3. Lewis and molecular structure (50% probability ellipsoids) of 2c.
in the Supporting Information) agree well with those obtained for Symmetry-related atoms are labeled with an apostrophe.
related sterically hindered borepins.[10d] The bonding parameters
of the carborane cluster, including the exocyclic B−C bonds (2a:
1.619(7) Å, 2b: 1.591(2) Å, 1: 1.595(3) Å), show no significant It should be emphasized that 9-borafluorene 1 exhibits much
differences from those of 1.[9] higher reactivity towards alkyne insertion than 9-aryl- or 9-halo-
substituted derivatives, which require elevated temperatures and

RESEARCH ARTICLE
longer reaction times to provide the insertion products. For trimethylsilyldiazomethane. Unlabeled vertices of the 1,2-dicarba-closo-
dodecaborane are BH units. Molecular structure of 3b (50% probability
example, Fukushima and coworkers reported that the bromo-
ellipsoids). Selected bond distances (Å) and angles (°) for 3b: B1−C1 1.690(3),
substituted 9-borafluorene underwent insertion of C1−C2 1.689(3), B1−C3 1.624(3), B1−C4 1.632(3), C4−Si1 1.901(2), B1−C6
diphenylacetylene within 12 h at 80 °C, while insertion product 2b 1.627(3), C6−N1 1.150(3), N1−N2 1.344(3), C3−B1−C4 110.1(18), B1−C4−C5
was formed quantitatively within a few minutes at room 110.3(18), C6−N1−N2 179.1(3).
temperature.[10d] The ease with which 1 undergoes alkyne
insertions is consistent with our previous work on alkene
insertions.[9] Nitrogen insertions. An established route to aromatic six-
In addition to these two-carbon insertion reactions, the membered 1,2-azaborinines is the ring expansion of boroles with
insertion of only one carbon atom into the borole ring has also organic azides, which act as nitrene transfer reagents after loss
been described.[11] The resulting boracyclohexadiene motif is of N2.[13] Accordingly, for 9-borafluorenes, the reaction leads to
readily accessible by reaction with diazomethanes, particularly 9,10-B,N-phenanthrene derivatives.[14] We tested compound 1 for
trimethylsilyldiazomethane.[11] Treatment of 1 with one equivalent this reactivity using a series of eight azides bearing aryl groups
Accepted Manuscript
of trimethylsilyldiazomethane produced the expected boracycle with different substitution patterns: phenyl, mesityl, 2,6-dibromo-
3a as a colorless solid in 62% yield (Figure 4). The 11B NMR 4-methyl-phenyl, 3,4,5-trifluorophenyl, 2-(trifluoromethyl)phenyl,
resonance at 69.8 ppm is consistent with the proposed central 4-nitrophenyl, 4-(dimethylamino)phenyl, and 4-methoxyphenyl
BC5 ring formation, which was further confirmed by X-ray azide. We found that both electron-withdrawing (F, Br, CF3, NO2)
diffraction analysis.[11a] Martin’s group has recently shown that and -donating substituents (Me, OMe, NMe 2) on the phenyl group
double carbon atom insertion is possible by adding two of the azide led to the formation of the respective B,N-
equivalents of the diazomethane reagent to 9-phenyl-9- phenanthrene derivatives in moderate to good yields (45% − 93%,
borafluorene.[11b] In our case, the seven-membered double Scheme 2). The 11B NMR signals of the (either colorless or yellow)
insertion product was not formed but rather a rearrangement of products 4a−h are found in a narrow range of 32.3 to 36.7 ppm,
the diazomethane reagent occurred at higher temperatures to which aligns well with reported values for other derivatives.[14]
form bis(trimethylsilyl)amino isocyanide, which was found to Moreover, their metric parameters, as determined by single-
coordinate to the boron atom of the single insertion product 3a crystal X-ray crystallography (Figure 5), are consistent with
(Figure 4). The base-stabilized 9,10-dihydro-9-boraphenanthrene previously characterized B,N-phenanthrene derivatives.[14] As for
derivative 3b, with a characteristic 11B NMR signal at −11.9 ppm, the carboranyl moiety, longer B1−C1 and C1−C2-bonds were
was obtained in a low isolated yield of 17% alongside unreacted observed in all B,N-phenanthrene derivatives (4a−h) relative to
3a (62%). The structure of 3b was confirmed by X-ray diffraction those of 9-borafluorene 1 (B1−C1: 1.648(3) − 1.657(2) Å vs.
of single crystals grown by slow diffusion of pentane into a 1.595(3) Å (1); C1−C2: 1.722(2)-1.699(3) Å vs. 1.666(3) Å (1)).
saturated solution of 3b in benzene (Figure 4). The isocyanide This is probably due to the presence of the electron-rich nitrogen
moiety is characterized by a C6−N1 bond distance of 1.150(3) Å atom in the ring, which imparts more electron density to both the
and a nearly linear C6−N1−N2 linkage, with a bond angle of neighboring boron atom and the carborane unit. Since the transfer
179.1(3)°. Its diagnostic C≡N stretching frequency is observed at of electron density to the carborane unit occurs in an antibonding
2265 cm−1 in the FT-IR spectrum. The reaction appears to be molecular orbital, the B1−C1 and C1−C2 bonds are weakened.
diastereoselective, as only one pair of enantiomers is formed.
Based on X-ray analysis, the two stereogenic centers (B1 and C4)
in 3b have either the (R,S) or (S,R) configuration. The unexpected
conversion of trimethylsilyldiazomethane to
bis(trimethylsilyl)amino isocyanide is reminiscent of isomerization
reactions of bis(trimethylsilyl)diazomethane described by
Wiberg.[12]
Scheme 2. Synthesis and isolated yields of the B,N-phenanthrene derivatives

4a-h.
Figure 4. Single carbon insertion into 9-borafluorene 1 to produce 3a and its

thermal conversion to 3b upon addition of further equivalents of

RESEARCH ARTICLE
Accepted Manuscript
Figure 6. Borole expansion by carbodiimide insertion. Unlabeled vertices of the
1,2-dicarba-closo-dodecaborane are BH units. Molecular structure of 5a and 5b
with selective atom labeling and thermal ellipsoids set at 50% probability. For
Figure 5. Representative examples of the molecular structures of the B,N- X-ray data and refinement statistics, see the Supporting Information.
phenanthrene derivatives (thermal ellipsoids are set at 50% probability;
hydrogen atoms have been omitted for clarity). For X-ray data and refinement
statistics, see the Supporting Information.
Similar ring expansion reactions were found for other
heteroallenes, such as isocyanates (RNCO) and thioisocyanates
(RNCS).[17,18] Despite the ambidentate character of the reagents,
It is worth noting that all reactions with the organic azides where either the nitrogen or oxygen atom can coordinate to the
proceed even at room temperature and do not require elevated Lewis acidic site of 1, leading to two different insertion products,
temperatures, as is usually the case with similar reactions we observed only the formal insertion of the carbon-nitrogen bond.
reported in the literature. Steric and electronic effects on the Compound 1 reacted with phenyl isocyanate and p-chlorophenyl
reaction rates were not readily apparent as all these isothiocyanate to afford boraheterocycles 6 and 7 in good yields
transformations proceeded within minutes at room temperature. of 69% and 93%, respectively (Figure 7). Interestingly, the sulfur
However, it is interesting to note that the substitution patterns of derivative 7 was isolated as a pink rather than a colorless solid.
the azides do not seem to affect the outcome of the reaction either, Single-crystal X-ray diffraction analysis confirmed the formation of
as 1,2-azaborinines are the only products. In the case of other a BNC5 ring with two vicinal aryl substituents and an exocyclic
monocyclic and annulated borole derivatives, divergent reaction (thio)carbonyl double bond. For compound 6, the C=O
pathways were often followed due to the steric and electronic functionality is also readily apparent in the FT-IR spectrum as a
properties of the organic azides.[11a,13b,13c,15] The substantial steric strong band at 1702 cm−1. The 11B NMR chemical shifts of 6
demand of the carborane substituent combined with the strong (δ(11B) = 50.0 ppm) and 7 (δ(11B) = 51.2 ppm) are similar and in
electrophilicity at the boron atom appear to direct the reaction of agreement with other derivatives.[17,18]
1 with organic azides to N2 loss and the selective formation of 1,2-
azaborinines.
One-carbon-homologated derivatives of 1,2-azaborinines
were shown to be accessible by reaction of boroles with
carbodiimides.[16] For example, as reported by Koley and So,
reaction of 9-chloro-9-borafluorene with N,N’-
dicyclohexylcarbodiimide (Cy−N=C=N−Cy) resulted in clean
conversion to the corresponding seven-membered BN
heterocycle in high yields.[16a] We carried out a similar reaction
with 9-borafluorene 1, using N,N’-dicyclohexyl- and N,N’-
diisopropylcarbodiimide. Separate treatment of 1 with these
carbodiimides in toluene solutions caused an instantaneous
reaction to generate products 5a and 5b, respectively, which were
obtained as colorless solids in good yields of 89 and 70%,
respectively (Figure 6). Single-crystal X-ray diffraction and NMR
analysis confirmed the expansion to seven-membered BNC5 rings
in which an unsaturated nitrogen–carbon moiety of the
carbodiimide had been inserted into an endocyclic boron-carbon
bond of 9-borafluorene 1. The 11B NMR resonances (37.2 for 5a;
37.4 ppm for 5b) and structural parameters are comparable to
Figure 7. Synthesis of 6 and 7 by (thio)isocyanate insertion. Molecular structure
those of reported derivatives.[16] The observed elongation of the of 7 with selective atom labeling and thermal ellipsoids set at 50% probability.
B1−C1 and C1−C2 bonds of the carborane moiety is similar to For X-ray data and refinement statistics of 7, see the Supporting Information.
that observed for B,N-phenanthrenes 4a−h, although less
pronounced.

RESEARCH ARTICLE
In addition to the nitrogen and/or carbon atom insertions into Phosphorus and oxygen insertions. Heteroatom insertions
the five-membered borole ring (see compounds 2-7 in Scheme 1), of phosphorus and oxygen atoms into borole rings have also been
we have attempted to expand the borole ring by insertion of a reported in the literature, resulting in an even greater variety of
RBNR unit using iminoboranes. Considering their isoelectronic accessible boron heterocycles.[16a,17,24] In order to test if 9-
relationship with alkynes,[19] we anticipated that they may undergo borafluorene 1 displays a similar reactivity to known borole
the same insertion reaction with borole 1, thereby giving BN derivatives, we treated it with a phosphaalkyne, two carbonyl
analogues of borepins as products. Although there is precedence compounds and a nitrone.
for this reaction with the related 9-aluminafluorenes,[20] a Treatment of 1 with one equivalent of 1-adamantyl
corresponding reaction has not yet been reported for borole phosphaalkyne at room temperature gave insertion product 9 with
derivatives. For boranes in general, however, such reactivity an 11B NMR resonance of 73.2 ppm (Figure 9). Together with the
31
towards iminoboranes is not new. As we have recently P NMR resonance at 205.3 ppm and a broad 13C NMR signal at
demonstrated, the iminoboranes (tert-butylimino)mesitylborane 127 ppm, the NMR data is consistent with formation of a 1,3-
(MesBNtBu) and di(tert-butyl)iminoborane (tBuBNtBu) readily phosphaborepin with an endocyclic P=C double bond.[24b] An X-
Accepted Manuscript
insert into the B−C bond of B(C6F5)3 to give diborylamines.[21] ray crystallographic analysis of yellow single crystals of 9
Using MesBNtBu, which was also used in the study of the 9- confirmed its formation. Like comparable structures, the seven-
aluminafluorenes, 9-borafluorene 1 underwent smooth ring membered BPC5 ring adopts a boat-like conformation.[24b] The
expansion at −78 °C, resulting in the dibenzoborepin derivative 8 P1−C3 distance (1.69(1) Å) and C3−P1−C4 angle (106.4(6)°) are
in 64% yield (Figure 8). In this case, low reaction temperatures consistent with a phosphaalkene moiety within the ring system. In
were required to prevent dimerization of the iminoborane the boat-like conformation, the vacant p orbital at the boron atom
reagent.[22] The connectivity of 8 involving a B−N−B linkage was and the π orbitals of the P=C double bond are misaligned,
confirmed by X-ray crystallography and heteronuclear NMR effectively eliminating any π conjugation.
spectroscopy. The two boron nuclei show 11B NMR signals at 65.3
and 39.5 ppm, with the chemical shift of the carboranyl-
substituted boron atom being barely affected by the ring
enlargement (1: δ(11B ) = 65.9 ppm). The ring heteroatoms form
an angle of B1−N−B2 = 110(2)°. The two B−N distances are
slightly different (B2−N1 1.408(17) Å; B1−N1 1.473(16) Å),
showing that the nitrogen atom is preferentially involved in π
bonding with the mesityl-substituted boryl group. This is also
reflected in the small torsion angle of 13.0(2)° between the mesityl
and the tert-butyl substituent at the nitrogen; the corresponding
angle to the carboranyl-bearing boryl group is 98.4(1)°. The
B2NC4 ring is strongly puckered, as evidenced by the twist angle
of 40.1° between the annulated benzene rings. As previously
observed for other heteroatom insertion products and adducts,
the C1−C2 bond (1.707(17) Å) of the carborane unit appears
slightly longer than that of 1 (C1−C2 1.666(3) Å). However, due
to the relatively poor quality of the X-ray diffraction data and Figure 9. Synthesis of and molecular structure (thermal ellipsoids set at 50%
probability) of 9. For X-ray data and refinement statistics, see the Supporting
associated high standard deviation in the bond distances, the Information.
difference is not statistically significant. Analogous seven-
membered azadiborepin ring systems have been reported
previously, however, these compounds were prepared by Reactions of 1 with benzaldehyde and benzophenone led to
different synthetic routes.[23] the successful insertion of the carbonyl group into the endocyclic
B−C bond of the central borole ring (10a, Figure 10). While the
reaction of 1 with benzaldehyde proceeded within minutes at
room temperature, the reaction with benzophenone was more
sluggish, requiring heating to 60 °C for 16 h to produce the
insertion product (10b, Figure 10). Monitoring the latter reaction
by NMR spectroscopy revealed initial reversible adduct formation
(δ(11B, 293 K) = 19.5 ppm; intermediate between three- and four-
coordinate boron),[26] followed by insertion and ring expansion at
elevated temperatures. Both products are colorless solids and
exhibit very similar 11B NMR chemical shifts (41.7 ppm for 10a;
41.8 ppm for 10b), consistent with a tricoordinate boron atom
bound to an oxygen substituent.[17b] These as well as the
structural data are in line with other unsaturated BOC 5
heterocycles reported by the group of Martin.[17b] Again, the mild
Figure 8. Borole expansion by iminoborane insertion. Unlabeled vertices of the
1,2-dicarba-closo-dodecaborane are BH units. Molecular structure of 8 with reaction conditions for ring expansion are noteworthy. For
selective atom labeling and thermal ellipsoids set at 50% probability. Selected comparison, Martin and coworkers noted that reaction for 10 days
bond distances (Å) and angles (°) for 8: B1−C1 1.608(18), C1−C2 1.707(17), at 100 °C was required for the quantitative insertion of
B1−C3 1.569(18), B1−N1 1.473(16), N1−B2 1.408(17), B2−C4 1.603(17),
diphenylketone into 9-phenyl-9-borafluorene.[17b]
C3−B1−N1 115.6(10), B1−N1−B2 110.2(10).
5

RESEARCH ARTICLE
Conclusion
In summary, 9-carboranyl-9-borafluorene is shown to react with

various unsaturated organic substrates via insertion and ring
expansion, leading to the formation of a broad spectrum of boron
heterocycles under very mild conditions. While related 9-aryl- and
9-halogen-substituted 9-borafluorenes have similar reactivity
profiles, reactions with the 9-carboranyl-substituted derivative are
more selective and occur under much milder conditions, in most
cases at room temperature and within minutes, illustrating the
strong influence of the electron-withdrawing o-carboranyl cage.
Accepted Manuscript
Experimental Section
General: All manipulations were performed either under an atmosphere of
dry argon or in vacuo using standard Schlenk line or glovebox techniques.
Figure 10. Borole ring expansion by carbonyl compounds. Molecular structures Deuterated solvents were dried over molecular sieves and degassed by
of 10a and 10b with selective atom labeling and thermal ellipsoids set at 50% three freeze-pump-thaw cycles prior to use. All other solvents were distilled
probability. See Supporting Information for more details.
and degassed from appropriate drying agents. Both deuterated and non-
deuterated solvents were stored under argon over activated 4 Å molecular
sieves. NMR spectra were acquired on a Bruker Avance 500 or a Bruker
In previous work, we have shown that nitrones, widely used Avance 400 NMR spectrometer. Chemical shifts (δ) are reported in ppm
1,3-dipolar compounds, can react with boroles with formal ONC and internally referenced to the carbon nuclei (13C{1H}) or residual protons
insertion to form eight-membered heterocycles.[24c] These (1H) of the solvent. Heteronuclei NMR spectra are referenced to external
products are reminiscent of the eight-membered BN3C4 standards (11B: BF3∙OEt2). General NMR numbering schemes are given in
the Supporting Information. Solid-state IR spectra were recorded on a
heterocycle isolated as an intermediate in the reaction of
Bruker FT-IR spectrometer ALPHA II inside a glovebox. Microanalyses (C,
pentaphenylborole with trimethylsilyl azide, another 1,3-dipole.[14b]
H, N, S) were performed on an Elementar vario MICRO cube elemental
When N,α-diphenylnitrone was used as the reagent, product 11 analyzer. High-resolution mass spectrometry (HRMS) data were obtained
formed in 92% yield in a spontaneous reaction at room from a Thermo Scientific Exactive Plus spectrometer. Unless otherwise
temperature (Figure 11). The yellow product has a 11B NMR noted, solvents and reagents were purchased from Sigma-Aldrich, Alfa
resonance at 46.2 ppm, in accord with the formation of an Aesar, VWR or TCI. 9-Borafluorene 1 was synthesized according to our
endocyclic boron-oxygen bond. The proton signal of the ring literature procedure.[9]
methine group was observed at 4.35 pm, which is shifted
significantly to lower frequencies compared to previously reported Synthesis of 2a: 9-borafluorene 1 (150 mg, 0.47 mmol) was dissolved in
compounds with a phenylated backbone (δ(1H) = 5.56–5.78).[24c] 3 mL of toluene and a solution of dry phenylacetylene (156 mg, 1.53 mmol)
in 1 mL of toluene was added slowly. The reaction mixture was stirred at
Its eight-membered ring structure, confirming the incorporation of
room temperature for 30 min before the reaction mixture was concentrated
all three atoms of the 1,3-dipole into the borole, was revealed by under vacuum. Addition of pentane (5 mL) resulted in precipitation of a
X-ray diffraction (Figure 11). Similar to other derivatives, the ring slightly orange solid. The solid was washed with pentane (10 x 1 mL) and
adopts a distorted boat conformation, with the boron atom dried in vacuo. Suitable crystals for X-ray diffraction analysis were
remaining in a trigonal-planar geometry (the sum of bond angles obtained by diffusion of pentane into a saturated benzene solution of 2a.
at B1 is 360.0(2)°).[24c] Yield: 74 mg (0.18 mmol, 37%) of a slightly orange solid. 1H{11B} NMR (500
MHz, C6D6): δ = 8.04 (dd, 1H, 3JHH = 7.7 Hz, 4J HH = 1.1 Hz, C2aryl−H), 7.60
(dd, 1H, 3JHH = 7.9 Hz, 4JHH = 0.7 Hz, C5aryl−H), 7.42 (dd, 1H, 3JHH = 7.9
Hz, 4JHH = 1.4 Hz, C11aryl−H), 7.25 (m, 1H, C4aryl−H), 7.22 (m, 3H,
C2+6phenyl−H/C8aryl−H), 7.16 (m, 1H, C3aryl−H), 7.07 (m, 1H, 3JHH = 7.3 Hz,
C4phenyl−H), 7.06 (m, 2H, C3+5phenyl−H), 7.03 (m, 1H, C10aryl−H), 6.94 (s,
1H, C14alkenyl−H), 6.89 (m, 1H, C9aryl−H), 3.22 (s, 1H, B−H), 3.01 (s, 2H,
B−H), 2.98 (s, 1H, B−H), 2.94 (s, 1H, B−H), 2.88 (s, 1H, B−H), 2.68 (s, 1H,
B−H), 2.61 (s, 1H, B−H), 2.41 (s, 1H, B−H), 2.39 (s, 1H, B−H), 0.88 (s, 3H,
CH3) ppm. 11B NMR (160 MHz, C6D6): δ = 64.9 (s, 1B, Bring), 1.9 (d, 1B,
B12), −4.6 (d, 1B, B7), −7.5 (d, 2B), −8.3 (d, 2B), −8.8 (d, 2B), −9.6 (d, 2B)
ppm. 13C{1H} NMR (126 MHz, C6D6): δ = 155.77 (s, 1C, C13alkenyl), 145.47
(s, 1C, C1aryl−B), 144.37 (s, 1C, C1phenyl), 144.29 (s,1C, C6aryl), 140.81 (s,
1C, C14alkenyl), 140.06 (s, 1C, C12aryl), 137.71 (s, 1C, C7aryl), 132.12 (s, 1C,
C11aryl), 131.66 (s, 1C, C4aryl), 131.15 (s, 1C, C8aryl), 130.50 (s, 1C, C5aryl),
129.52 (s, 1C, C2aryl), 129.02 (s, 2C, C2+6phenyl), 128.81 (s, 1C, C4phenyl),
128.66 (s, 2C, C3+5phenyl), 127.98 (s, 1C, C10aryl), 127.07 (s, 1C, C9aryl),
126.94 (s, 1C, C3aryl), 77.14 (s, 1C, Ccage−CH3), 74.47 (s, 1C, Ccage−B),
24.28 (s, 1C, Ccage−CH3) ppm. HRMS (LIFDI): calcd. for 2a: m/z =
Figure 11. Ring expansion of 1 with diphenylnitrone. Molecular structure of 11
422.3209; found: m/z = 422.3204. Elemental analysis (%) calcd. for
with selective atom labeling and thermal ellipsoids set at 50% probability (see
Supporting Information for details). C29H31B11: C 65.40, H 6.44; found: C 65.25, H 6.48. IR spectroscopy [ṽ]:
3051 cm−1 (Caryl−H, w), 2570 cm-1 (B−H, s), 1581 cm-1 (C=C, s), 1442
cm-1 (C=C, s).

RESEARCH ARTICLE
Synthesis of 2b: 9-borafluorene 1 (150 mg, 0.47 mmol) was dissolved in solid. 1H{11B} NMR (500 MHz, C6D6): δ = 8.13 (d, 1H, 3JHH = 7.7 Hz,
3 mL of toluene and diphenylacetylene (84 mg, 0.47 mmol) dissolved in C2aryl−H), 7.67 (m, 2H, C5+11aryl−H), 7.27 (ddd, 2H, 3JHH = 7.9 Hz, 4JHH =
1 mL of toluene was added slowly. The reaction mixture was stirred at 1.4 Hz, C4aryl−H), 7.06 (m, 3H, C3+9+10aryl−H), 6.92 (m, 1H, C8aryl−H),
room temperature for 1 h before the reaction mixture was concentrated 3.84 (s, 1H, Si−C13alkyl−H), 3.25 (s, 1H, B−H), 3.06 (s, 3H, B−H), 2.97 (s,
under vacuum. The addition of hexane (5 mL) resulted in precipitation of a 1H, B−H), 2.91 (s, 1H, B−H), 2.84 (s, 1H, B−H), 2.78 (s, 1H, B−H), 2.44 (s,
colorless solid, which was washed with hexane (10 x 1 mL) and dried in 2H, B−H), 0.81 (s, 3H, CH3), −0.34 (s,9H, Si(CH3)3) ppm. 11B NMR
vacuo. Suitable crystals for X-ray diffraction analysis were obtained by (160 MHz, C6D6): δ = 69.8 (s, 1B, Bring), 1.7 (d, 1B, B12), −4.6 (d, 1B, B7),
diffusion of hexane into a saturated benzene solution of 2b. Yield: 146 mg −7.6 (d, 2B), −8.0 (d, 3B), −9.2 (d, 1B), −9.8 (d, 1B), −10.4 (d, 1B) ppm.
(0.29 mmol, 62%) of a colorless solid. 1H{11B} NMR (500 MHz, C6D6): δ = 13C{1H} NMR (126 MHz, C D ): δ = 144.21 (s, 1C, C6
6 6 aryl), 137.74 (s, 1C,
7.49 (d, 1H, 3JHH = 7.7 Hz, C5aryl−H), 7.38 (dm, 2H, 3JHH = 7.8 Hz, C2aryl−H/ C7aryl), 136.16 (s, 1C, C1aryl−B), 134.30 (s,1C, C4aryl), 133.49 (s, 1C,
C8aryl−H), 7.25 (dd, 1H, 3JHH = 7.5 Hz, 4JHH = 1.5 Hz, Cphenyl−H), 7.23 (dt C12aryl), 133.16 (s, 1C, C2aryl), 128.61 (s, 1C, C9aryl), 127.77 (s, 1C, C8aryl),
1H, 3JHH = 7.7 Hz, 4J HH = 1.4 Hz, C4aryl−H), 7.14 (dt, 1H, 3JHH = 7.5 Hz, 4J HH 126.76 (s, 1C, C3aryl), 125.32 (s, 1C, C10aryl), 125.21 (s, 1C, C11aryl),
= 1.1 Hz, C3aryl−H), 7.10 (m, 2H, C11aryl−H/ Cphenyl−H), 6.90 (m, 8H, 124.44 (s, 1C, C5aryl), 77.58 (s, 1C, Ccage−CH3), 75.85 (s, 1C, Ccage−B),
C9+10aryl−H/Cphenyl−H), 6.80 (m, 2H, Cphenyl−H), 3.19 (s, 1H, B−H), 2.85 (s, 53.71 (s, 1C, C13aryl−Si(CH3)3), 24.09 (s, 1C, Ccage−CH3), −0.45 (s, 3C,
1H, B−H), 2.82 (s, 2H, B−H), 2.60 (s, 1H, B−H), 2.41 (s, 1H, B−H), 2.39 (s, Si(CH3)3) ppm. 29Si NMR (99.4 MHz, C6D6): δ = 6.37 (s, 1Si, Si(CH3)3) ppm.
Accepted Manuscript
1H, B−H), 2.33 (s, 2H, B−H), 2.04 (s, 1H, B−H), 1.17 (s, 3H, CH3) ppm. IR spectroscopy [ṽ]: 3059 cm-1 (Caryl−H, w), 2954 cm-1 (Calkyl−H, m),
11B NMR (160 MHz, C D ): δ = 73.8 (s, 1B, B
6 6 ring), 3.1 (d, 1B, B12), −4.8 (d, 2570 cm-1 (B−H, s), 1593 cm-1 (C=C, w), 1483 cm-1 (C=C, m), 1436 cm-1
1B, B7), −7.1 (d, 2B), −7.4 (d, 2B), −8.2 (d, 2B), −9.3 (d, 2B) ppm. 13C{1H} (C=C, m).
NMR (126 MHz, C6D6): δ = 150.45 (s, 1C, C14alkenyl), 148.54 (s, 1C,
C1aryl−B), 141.18 (s, 1C, C12aryl), 140.87 (s,1C, C1phenyl), 140.00 (s, 1C, Synthesis of 3b: 9-borafluorene 1 (150 mg, 0.47 mmol) was dissolved in
C6aryl), 138.74 (s, 1C, C7aryl), 137.89 (s, 1C, C13aryl), 137.11 (s, 1C, C1aryl), 3 mL of toluene and a solution of trimethylsilyldiazomethane (228 mg,
131.26 (s, 1C, C8aryl), 131.23 (s, 1C, Cphenyl), 130.81 (s, 2C, Cphenyl), 130.28 2.0 mmol, 2 M in hexane, 1.0 mL) in 2 mL of toluene was added dropwise.
(s, 1C, C4aryl), 130.27 (s, 2C, Cphenyl), 129.36 (s, 1C, C5aryl), 128.37 (s, 2C, The reaction mixture was stirred at room temperature for 1 h and 15 h at
Cphenyl), 128.35 (s, 1C, C11aryl), 127.93 (s, 2C, Cphenyl), 127.62 (s, 1C, 60 °C before it was concentrated under vacuum. The addition of pentane
C9+10aryl/Cphenyl), 127.54 (s, 1C, C9+10Aryl/Cphenyl), 127.12 (s, 1C, Cphenyl), (3 mL) resulted in precipitation of a colorless solid, which was washed with
127.04 (s, 1C, C3aryl), 125.32 (s, 1C, C2aryl), 78.06 (s, 1C, Ccage−CH3), pentane (5x 1 mL) and dried in vacuo. Suitable crystals for X-ray diffraction
73.72 (s, 1C, Ccage−B), 24.97 (s, 1C, Ccage−CH3) ppm. HRMS (LIFDI): calcd. analysis were obtained by slow diffusion of pentane into a saturated
for 2b: m/z = 498.3522; found: m/z = 498.3511. Elemental analysis (%) benzene solution of 3b. Yield: 47 mg (0.08 mmol, 17%) of a colorless solid.
calcd. for C23H27B11: C 69.88, H 6.27; found: C 69.84, H 6.44. IR 1H{11B} NMR (500 MHz, C D ): δ = 7.66 (dm, 1H, 3J
6 6 HH = 7.8 Hz, C5aryl−H),
spectroscopy [ṽ]: 3053 cm-1 (Caryl−H, w), 2555 cm-1 (B−H, s), 1584 cm-1 7.59 (dd, 1H, 3JHH = 7.2 Hz, 4JHH = 1.6 Hz, C2aryl−H), 7.48 (dm, 1H, 3J HH =
(C=C, s), 1432 cm-1 (C=C, s). 7.7 Hz, C8aryl−H), 7.27 (td, 1H, 3JHH = 7.5 Hz, 4JHH = 1.6 Hz, C4aryl−H), 7.18
(td, 1H, 3JHH = 7.2 Hz, 4JHH = 1.2 Hz, C3aryl−H), 7.10 (m, 1H, C10aryl−H),
Synthesis of 2c: 9-borafluorene 1 (150 mg, 0.47 mmol) was dissolved in 7.07 (m, 1H, C11aryl−H), 7.02 (m, 1H, C9aryl−H), 3.11 (s, 1H, B−H), 2.96 (s,
3 mL of toluene and a solution of dry 1,5-hexadiyne (19 mg, 0.24 mmol) in 2H, B−H), 2.89 (s, 1H, B−H), 2.83 (s, 1H, B−H), 2.78 (s, 1H, B−H), 2.71 (s,
2 mL of toluene was added slowly. The reaction mixture was stirred at 1H, B−H), 2.58 (s, 1H, B−H), 2.51 (s, 1H, B−H), 2.42 (s, 1H, B−H), 2.12 (s,
room temperature for 1 h before the reaction mixture was concentrated 1H, Si−C13alkyl−H), 0.95 (s, 3H, CH3), 0.04 (s,18H, CNN[Si(CH3)3]2), −0.20
under vacuum. The addition of hexane (5 mL) resulted in precipitation of a (s,9H, C13alkyl−Si(CH3)3) ppm. 11B NMR (160 MHz, C6D6): δ = −1.3 (d, 1B,
slightly yellow solid. The solid was washed with hexane (10 x 1 mL) and B12), −5.3 (d, 1B, B7), −7.4 (d, 2B), −8.3 (d, 2B), −9.0 (d, 2B), −9.8 (d, 2B),
dried in vacuo. Suitable crystals for X-ray diffraction analysis were −11.9 (s, 1B, Bring) ppm. 13C{1H} NMR (126 MHz, C6D6): δ = 142.89 (s, 1C,
obtained by slow evaporation of a saturated solution of 2c in toluene. Yield: C6aryl), 141.45 (s, 1C, C12aryl), 139.91 (s, 1C, C1aryl−B), 137.52 (s,1C,
57 mg (0.08 mmol, 33%) of a slightly yellow solid. 1H{11B} NMR (500 MHz, C7aryl), 136.29 (s, 1C, C2aryl), 132.90 (s, 1C, C11aryl), 128.51 (s, 1C, C4aryl),
C6D6): δ = 7.73−7.30 (m, 16H, Caryl−H), 6.05 (s, 2H, C14alkenyl−H), 3.26 (d, 127.40 (s, 1C, C10aryl), 125.98 (s, 1C, C3aryl), 125.58 (s, 1C, C8aryl), 125.01
2H, 3JHH = 8.7 Hz, CHH), 2.45 (m, 2H, CHH), 2.43 (s, 2H, B−H), 2.26 (s, (s, 1C, C9aryl), 123.77 (s, 1C, C5aryl), 105.22 (s, 1C, CNN[Si(CH3)3]2), 84.73
6H, B−H), 2.21 (s, 2H, B−H), 2.06 (s, 2H, B−H), 1.07 (s, 6H, CH3) ppm. (s, 1C, Ccage−B), 78.67 (s, 1C, Ccage−CH3), 31.11 (s, 1C, C13aryl−Si(CH3)3),
11B NMR (160 MHz, C D ): δ = 65.7 (s, 2B, B
6 6 ring), 0.8 (d, 1B, B12), −5.5 (d, 24.34 (s, 1C, Ccage−CH3), 0.47 (s, 6C, N[Si(CH3)3]2), 0.19 (s, 3C,
1B, B7), −8.5 (d, 4B), −10.3 (d, 4B) ppm. 13C{1H} NMR (126 MHz, C6D6): C13aryl−Si(CH3)3) ppm. 29Si NMR (99.4 MHz, C6D6): δ = 23.90 (s, 2Si,
δ = 153.25 (s, 2C, C1aryl−B), 144.12 (s, 2C, Caryl), 140.01 (s, 2C, CNN[Si(CH3)3]2), 3.00 (s, 1Si, C13aryl−Si(CH3)3) ppm. Elemental analysis
C14alkenyl−B), 136.47 (s,2C, C13alkenyl), 132.79 (s, 2C, Caryl−H), 131.39 (s, (%) calcd. for C26H49B11N2Si3: C 52.67, H 8.33, N 4.73; found: C 53.04, H
2C, Caryl−H), 130.03 (s, 2C, Caryl−H), 129.51 (s, 2C, Caryl−H), 128.49 (s, 2C, 8.33, N 4.72. IR spectroscopy [ṽ]: 3055 cm-1 (Caryl−H, w), 2954 cm-1
Caryl), 127.70 (s, 2C, Caryl-H), 127.48 (s, 2C, Caryl−H), 126.66 (s, 2C, (Calkyl−H, m), 2565 cm-1 (B−H, s), 2265 cm-1 (C≡N, s), 1593 cm-1 (C=C, w),
Caryl−H), 126.44 (s, 2C, Caryl−H), 76.67 (s, 2C, Ccage−CH3), 73.96 (s, 2C, 1471 cm-1 (C=C, w), 1443 cm-1 (C=C, m).
Ccage−B), 39.03 (s, 2C, CH2), 24,73 (s, 2C, Ccage−CH3) ppm. HRMS
(LIFDI): calcd. for 2c: m/z = 718.5948; found: m/z = 718.5929. Elemental General procedure for the preparation of the B,N-phenanthrene
analysis (%) calcd. for C36H48B22: C 60.17, H 6.73; found: C 59.88, H 6.66. derivatives 4a-h: 9-borafluorene 1 (150 mg, 0.47 mmol) was dissolved in
IR spectroscopy [ṽ]: 3057 cm-1 (Caryl−H, w), 2574 cm-1 (B−H, s), 1587 cm-1 3 mL of benzene and a solution of the aryl azide (0.47 mmol) in 1 mL of
(C=C, s), 1443 cm-1 (C=C, s). Annotation: 2c exists as two diastereomers benzene was added slowly. The reaction mixture was stirred at room
in solution (ratio ca. 7:3). Only the signals corresponding to the main temperature for 30 min before it was concentrated under vacuum. The
product were assigned. Further assignments were not possible due to addition of hexane (5 mL) resulted in precipitation of a colorless solid. The
signal overlaps in the 1H NMR spectrum. solid was washed with hexane (10 x 1 mL) and dried in vacuo. In most
cases, suitable crystals for X-ray diffraction analysis were obtained by slow
Synthesis of 3a: 9-borafluorene (1, 150 mg, 0.47 mmol) was dissolved in evaporation of a saturated solution in benzene.
3 mL of toluene and a solution of trimethylsilyldiazomethane (54 mg,
0.47 mmol, 2 M in hexane, 0.24 mL) in 2 mL of toluene was added slowly. 4a: Yield: 119 mg (0.29 mmol, 62%) of a colorless solid. 1H{11B} NMR
The reaction mixture was stirred at room temperature for 1 h before it was (500 MHz, C6D6): δ = 9.55 (d, 1H, 3JHH = 8.3 Hz, C2aryl−H), 8.23 (d, 1H,
concentrated under vacuum. Addition of pentane (10 mL) resulted in 3J
HH = 8.1 Hz, C5aryl−H), 8.20 (dd, 1H, JHH = 8.1 Hz, JHH = 1.5 Hz,
3 4
precipitation of a colorless solid, which was washed with pentane (5 x C8aryl−H), 7.43 (ddd, 1H, 3JHH = 8.5 Hz, 4JHH = 1.2 Hz, C4aryl−H), 7.33 (ddd,
1 mL) and dried in vacuo. Suitable single crystals for X-ray diffraction 1H, 3JHH = 8.5 Hz, 4JHH = 1.2 Hz, C3aryl−H), 7.07 (s, 1H, Cphenyl−H), 7.05
analysis were obtained by slow diffusion of pentane into a saturated (ddd, 1H, 3JHH = 8.5 Hz, 4JHH = 1.2 Hz, C9aryl-H), 6.95 (s, 1H, Cphenyl−H),
benzene solution of 3a. Yield: 119 mg (0.29 mmol, 62%) of a colorless
7

RESEARCH ARTICLE
6.94 (ddd, 1H, 3JHH = 8.5 Hz, 4JHH = 1.6 Hz, C10aryl-H), 6.79 (s, 1H, HH = 8.2 Hz, JHH = 1.3 Hz, C4aryl−H), 7.29 (dd, 1H, J HH = 8.3 Hz, JHH =
3J 4 3 4
Cphenyl−H), 6.68 (dd, 1H, 3JHH = 8.7 Hz, 4JHH =1.1 Hz, C11Aryl−H), 6.60 (s, 1.2 Hz, C3aryl−H), 7.11 (dd, 1H, 3JHH = 8.4 Hz, 4JHH = 1.3 Hz, C9aryl−H),
1H, Cphenyl−H), 3.46 (s, 1H, B−H), 3.37 (s, 1H, B−H), 3.21 (s, 2H, B−H), 7.06 (dd, 1H, 3JHH = 8.6 Hz, 4JHH = 1.7 Hz, C10aryl−H), 6.34 (dd, 1H, 3JHH =
2.95 (s, 2H, B−H), 2.75 (s, 1H, B−H), 2.55 (s, 1H, B−H), 2.43 (s, 1H, B−H), 8.6 Hz, 4JHH = 1.1 Hz, C11aryl−H), 6.12 (s, 1H, C2/6phenyl−H), 6.06 (s, 1H,
2.25 (s, 1H, B−H), 1.18 (s, 3H, CH3) ppm. 11B NMR (160 MHz, C6D6): δ = C2/6phenyl−H), 3.34 (s, 1H, B−H), 3.27 (s, 1H, B−H), 3.19 (s, 2H, B−H), 2.91
32.3 (s, 1B, Bring), 2.4 (d, 1B), −5.1 (d, 1B), −7.5 (d, 6B), −8.9 (d, 2B) ppm. (s, 2H, B−H), 2.74 (s, 1H, B−H), 2.50 (s, 1H, B−H), 2,25 (s, 1H, B−H), 2.20
13C{1H} NMR (126 MHz, C D ): δ = 143.16 (s, 1C, C1
6 6 phenyl), 141.93 (s, 1C, (s, 1H, B−H), 1.00 (s, 3H, CH3) ppm. 11B NMR (160 MHz, C6D6): δ = 33.0
C12aryl), 140.09 (s, 1C, C6aryl), 138.81 (s, 2C, C1+2aryl), 131.78 (s, 1C, (s, 1B, Bring), 2.7 (d, 1B), −5.0 (d, 1B), −7.3 (d, 6B), −9.0 (d, 2B) ppm.
13C{1H} NMR (126 MHz, C D ): δ = 152.93 (d, 1C, 2J
Cphenyl), 131.68 (s, 1C, C4aryl), 130.99 (s, 1C, Cphenyl), 130.40 (s, 1C, Cphenyl), 6 6 CF = 76.2 Hz,
129.11 (s, 1C, C9aryl), 128.87 (s, 1C, Cphenyl), 127.93 (s, 1C, C10aryl), C3/5phenyl), 150.91 (d, 1C, 2J CF = 76.2 Hz, C3/5phenyl), 140.88 (s, 1C, C12aryl),
125.78 (s, 1C, C3aryl), 123.94 (s, 1C, C8aryl), 123.62 (s, 1C, C9aryl), 122.69 139.85 (s, 1C, C6aryl), 138.85 (s, 1C, C2aryl), 138.30 (s, 1C, C4phenyl), 132.18
(s, 1C, C5aryl), 120.66 (s, 1C, C11aryl), 78.27 (s, 1C, Ccage−CH3), 71.42 (s, (s, 1C, C4aryl), 129.70 (s, 1C, C1aryl−B), 128.53 (s, 1C, C1phenyl), 128.24 (s,
1C, Ccage−B), 25.28 (s,1C, Ccage−CH3) ppm. HRMS (LIFDI): calcd. for 4a: 1C, C10aryl), 126.04 (s, 1C, C3aryl), 125.08 (s, 1C, C7aryl), 124.18 (s, 1C,
m/z = 411.3161; found: m/z = 411.3148. Elemental analysis (%) calcd. for C8aryl), 124.13 (s, 1C, C9aryl), 122.68 (s, 1C, C5aryl), 119.88 (s, 1C, C11aryl),
C21H26B11N: C 61.32, H 6.37, N 3.41; found: C 61.32, H 6.61, N 2.95. 117.24 (d, 1C, 2JCF = 17.5 Hz, C2/6phenyl), 115.72 (d, 1C, 2JCF = 17.5 Hz,
Accepted Manuscript
C2/6phenyl), 78.39 (s, 1C, Ccage−CH3), 74.61 (s, 1C, Ccage−B), 25.18 (s,1C,
4b: Yield: 157 mg (0.35 mmol, 74%) of a colorless solid. 1H{11B} NMR Ccage−CH3) ppm. 19F{1H} NMR (471 MHz, C6D6): δ = −132.17 (d, 2F,
(500 MHz, C6D6): δ = 9.30 (dd, 1H, 3J HH = 8.3 Hz, 4JHH = 1.1 Hz, C2aryl−H), C3/5Phenyl−F), -157.93 (tm, 1F, C4Phenyl−F) ppm. HRMS (LIFDI): calc. for
8.23 (d, 1H, 3JHH = 8.4 Hz, 4JHH = 1.6 Hz, C8aryl−H), 8.18 (dd, 1H, 3JHH = 4d: m/z = 465.2879; found: m/z = 465.2866. IR spectroscopy [ṽ]: 3059
8.2 Hz, C5aryl−H), 7.42 (dd, 1H, 3JHH = 8.6 Hz, 4JHH = 1.4 Hz, C4aryl−H), cm-1 (Caryl−H, w), 2930 cm-1 (Calkyl−H, w), 2543 cm-1 (B−H, s), 1621 cm-1
7.27 (dd, 1H, 3JHH = 8.3 Hz, 4JHH = 1.2 Hz, C3aryl−H), 7.06 (dd, 1H, 3JHH = (C=C, s), 1522 cm-1 (C=C, s), 1445 cm-1 (C=C, s).
8.3 Hz, 4JHH = 1.2 Hz, C9aryl−H), 6.97 (dd, 1H, 3JHH = 8.8 Hz, 4JHH = 1.6 Hz,
C10aryl−H), 6.74 (s, 2H, C3/5mesityl−H), 6.71 (dd, 1H, 3JHH = 8.7 Hz, 4JHH = 4e: Yield: 182 mg (0.28 mmol, 81%) of a yellow solid. 1H{11B} NMR
1.1 Hz, C11aryl−H), 3.42 (s, 2H, B−H), 3.21 (s, 2H, B−H), 2-92 (s, 2H, B−H), (500 MHz, CD2Cl2): δ = 8.87 (s, 1H, C2aryl−H), 8.48 (dd, 1H, 3J HH = 7.3 Hz,
2.75 (s, 2H, B−H), 2.47 (s, 2H, B−H), 2.12 (s, 3H, C4mesityl−CH3), 1.70 (br, 4J
HH = 2.0 Hz, C8aryl−H), 8.43 (d, 1H, JHH = 8.0 Hz, C5aryl−H), 7.87 (m, 1H,
3
6H, C2/6mesityl−CH3), 1.14 (s, 3H, CH3) ppm. 11B NMR (160 MHz, C6D6): C2phenyl−H), 7.85 (m, 2H, C3+4phenyl−H), 7.81 (ddd, 1H, 3JHH = 7.5 Hz, 4JHH
δ = 34.3 (s, 1B, Bring), 2.1 (d, 1B), −5.0 (d, 1B), −7.5 (d, 4B), −8.4 (d, 2B), = 1.4 Hz, C4aryl−H), 7.75 (m, 1H, C5phenyl−H), 7.59 (ddd, 1H, 4JHH = 1.1 Hz,
−9.7 (d, 2B) ppm. 13C{1H} NMR (126 MHz, C6D6): δ = 139.71 (s, 1C, C6aryl), C3aryl−H), 7.34 (m, 2H, C9+10aryl−H), 6.83 (d, 1H, 3JHH = 6.9 Hz, C11aryl−H),
139.54 (s, 1C, C12aryl), 138.79 (s, 1C, C1mesityl), 138.17 (s, 1C, C2aryl), 3.19 (s, 1H, B−H), 2.71 (s, 1H, B−H), 2.59 (s, 1H, B−H), 2.37 (s, 2H, B−H),
137.69 (s, 1C, C1aryl−B), 137.47 (s, 2C, C2+6mesityl), 131.78 (s, 1C, C4aryl), 2.13 (s, 1H, B−H), 2.11 (s, 1H, B−H), 2.03 (s, 2H, B−H), 1,97 (s, 1H, B−H),
130.55 (s, 1C, C3/5mesityl), 129.38 (s, 1C, C3/5mesityl), 128.67 (s, 1C, C10aryl), 1.49 (s, 3H, CH3) ppm. 11B NMR (160 MHz, CD2Cl2): δ = 36.7 (s, 1B, Bring),
128.53 (s, 1C, C4mesityl), 125.31 (s, 1C, C3aryl), 125.27 (s, 1C, C7aryl), 2.4 (d, 1B), −4.7 (d, 1B), −7.3 (d, 2B), −8.2 (d, 4B), −9.1 (d, 2B) ppm.
13C{1H} NMR (126 MHz, CD Cl ): δ = 141.05 (s, 1C, C12
124.15 (s, 1C, C8aryl), 123.62 (s, 1C, C9aryl), 122.60 (s, 1C, C5aryl), 118.60 2 2 aryl), 139.41 (s,
(s, 1C, C11aryl), 79.66 (s, 1C, Ccage−CH3), 75.36 (s, 1C, Ccage-B), 25.15 (s, 1C, C6aryl), 138.93 (s, 1C, C6phenyl), 137.02 (s, 2C, C2aryl/C3/4phenyl), 132.21
1C, Ccage−CH3), 20.98 (s,1C, C4mesityl−CH3), 19.15 (s, 2C, C2mesityl−CH3) (s, 1C, C4aryl), 131.82 (s, 1C, C2phenyl), 130.31 (s/q, 2C, C1aryl−B/CF3),
ppm. HRMS (LIFDI): calcd. for 4b: m/z = 453.3631; found: m/z = 453.3621. 129.97 (s, 1C, C5phenyl), 128.95 (s, 1C, C9/10aryl), 128.28 (s, 1C, C3/4phenyl),
Elemental analysis (%) calcd. for C24H32B11N: C 63.57, H 7.11, N 3.09; 125.59 (s, 1C, C3aryl), 124.42 (s, 2C, C7+8aryl), 123.67 (s, 1C, C9/10aryl),
found: C 63.07, H 6.83, N 2.95. IR spectroscopy [ṽ]: 3065 cm-1 (Caryl−H, w), 123.07 (s, 1C, C5aryl), 118.29 (s, 1C, C11aryl), 79.41 (s, 1C, Ccage−CH3),
2565 cm-1 (B−H, s), 1598 cm-1 (C=C, s), 1479 cm-1 (C=C, s), 1432 cm-1 74.52 (s, 1C, Ccage−B), 25.28 (s,1C, Ccage−CH3) ppm. 19F{1H} NMR (471
(C=C, s). MHz, CD2Cl2): δ = −59.99 (s, C2phenyl−CF3) ppm. HRMS (LIFDI): calcd. for
4e: m/z = 479.3035; found: m/z = 479.3020. Elemental analysis (%) calcd.
4c: Yield: 255 mg (0.44 mmol, 93%) of a colorless solid. 1H{11B} NMR for C22H25B11NF3: C 55.12, H 5.26, N 2.92; found: C 55.86, H 5.09, N 3.24.
(500 MHz, C6D6): δ = 9.34 (d, 1H, 3JHH = 7.9 Hz, C2aryl−H), 8.19 (d, 1H, IR spectroscopy [ṽ]: 3061 cm-1 (Caryl−H, w), 2932 cm-1 (Calkyl−H, w),
3J
HH = 7.7 Hz, JHH = 1.6 Hz, C8aryl−H), 8.13 (dd, 1H, JHH = 8.1 Hz,
4 3 2570 cm-1 (B−H, s), 1599 cm-1 (C=C, s), 1487 cm-1 (C=C, s), 1439 cm-1
C5aryl−H), 7.41 (dd, 1H, 3JHH = 8.4 Hz, 4JHH = 1.2 Hz, C4aryl−H), 7.26 (dd, (C=C, s).
1H, 3JHH = 8.5 Hz, 4JHH = 1.1 Hz, C3aryl−H), 7.07 (dd, 1H, 3JHH = 8.3 Hz,
4
JHH = 1.4 Hz, C9aryl−H), 7.03 (dd, 1H, 3JHH = 8.6 Hz, 4J HH = 1.6 Hz, 4f: Yield: 167 mg (0.37 mmol, 78%) of a colorless solid. 1H{11B} NMR
C10aryl−H), 7.00 (s, 2H, C3/5phenyl−H), 6.68 (dd, 1H, 3JHH = 8.5 Hz, 4JHH = (500 MHz, C6D6): δ = 9.27 (dd, 1H, 3J HH = 8.3 Hz, 4JHH = 1.0 Hz, C2aryl−H),
1.4 Hz, C11aryl−H), 3.48 (s, 2H, B−H), 3.24 (s, 2H, B−H), 2.99 (s, 1H, B−H), 8.55 (d, 1H, 3JHH = 8.4 Hz, C5aryl−H), 8.54 (d, 1H, 3JHH = 8.4 Hz, C8aryl−H),
2.76 (s, 1H, B−H), 2.62 (s, 1H, B−H), 2.54 (s, 2H, B−H), 2.47 (s, 1H, B−H), 8.48 (d, 2H, 3JHH = 8.3 Hz, C3/5phenyl−H), 7.84 (dd, 1H, 3JHH = 8.5 Hz, 4J HH
1.66 (s, 3H, C4phenyl−CH3), 1.38 (s, 3H, CH3) ppm. 11B NMR (160 MHz, = 1.4 Hz, C4aryl−H), 7.65 (dd, 1H, 3J HH = 8.4 Hz, 4J HH = 1.2 Hz, C3aryl−H),
C6D6): δ = 35.3 (s, 1B, Bring), 2.5 (d, 1B), -−4.8 (d, 1B), −7.0 (d, 2B), −7.9 7.52 (s, 2H, 3JHH = 7.4 Hz, C2/6phenyl−H), 7.40 (dd, 1H, 3JHH = 8.3 Hz, 4JHH
(d, 4B), −9.4 (d, 2B) ppm. 13C{1H} NMR (126 MHz, C6D6): δ = 142.33 (s, = 1.2 Hz, C9aryl−H), 7.31 (dd, 1H, 3JHH = 8.7 Hz, 4JHH = 1.6 Hz, C10aryl−H),
1C, C4phenyl), 139.78 (s, 1C, C6aryl), 138.58 (s, 1C, C2aryl), 138.19 (s, 1C, 6.62 (dd, 1H, 3JHH = 8.7 Hz, 4JHH = 1.0 Hz, C11aryl−H), 3.14 (s, 1H, B−H),
C12aryl), 137.71 (s, 1C, C1phenyl), 133.88 (s, 1C, C3/5phenyl), 133.30 (s, 1C, 3.01 (s, 1H, B−H), 2.51 (s, 1H, B−H), 2.47 (s, 1H, B−H), 2.24 (s, 1H, B−H),
C3/5phenyl), 132.18 (s, 1C, C4aryl), 130.12 (s, 1C, C1aryl−B), 128.57 (s, 1C, 2.15 (s, 1H, B−H), 2.07 (s, 2H, B−H), 1.98 (s, 1H, B−H), 1.67 (s, 3H, CH3),
C10aryl), 125.33 (s, 1C, C3aryl), 125.29 (s, 1C, C7aryl), 124.38 (s, 1C, C8aryl), 1.10 (s, 1H, B−H) ppm. 11B NMR (160 MHz, C6D6): δ = 33.7 (s, 1B, Bring),
123.97 (s, 1C, C9aryl), 122.58 (s, 1C, C5aryl), 118.45 (s, 1C, C11aryl), 80.15 2.1 (d, 1B), −5.6 (d, 1B), −7.8 (d, 6B), −9.3 (d, 2B) ppm. 13C{1H} NMR
(s, 1C, Ccage−CH3), 74.57 (s, 1C, Ccage−B), 25.25 (s,1C, Ccage−CH3), 20.17 (126 MHz, C6D6): δ = 148.61 (s, 1C, C1/4phenyl), 147.95 (s, 1C, C1/4phenyl),
(s,1C, C4phenyl−CH3) ppm. HRMS (LIFDI): calcd. for 4c: m/z = 583.1508; 140.38 (s, 1C, C12aryl), 139.52 (s, 1C, C6aryl), 138.31 (s, 1C, C2aryl), 132.76
found: m/z = 583.1497. Elemental analysis (%) calcd. for C22H26B11NBr2: (s, 2C, C2+6phenyl), 132.08 (s, 1C, C4aryl), 129.24 (s, 1C, C1aryl−B), 128.32
C 45.31, H 4.49, N 2.40; found: C 45.74, H 4.66, N 2.63. IR spectroscopy (s, 1C, C10aryl), 125.78 (s, 1C, C3aryl), 124.67 (s, 1C, C7aryl), 124.10 (s, 2C,
[ṽ]: 3059 cm-1 (Caryl−H, w), 2563 cm-1 (B−H, s), 1600 cm-1 (C=C, s), C8+9aryl), 122.57 (s, 1C, C5aryl), 119.43 (s, 1C, C11aryl), 78.08 (s, 1C,
1486 cm-1 (C=C, s), 1439 cm-1 (C=C, s). Ccage−CH3), 74.06 (s, 1C, Ccage−B), 25.59 (s,1C, Ccage−CH3) ppm. HRMS
(LIFDI): calcd. for 4f: m/z = 456.3012; found: m/z = 456.3003. Elemental
4d: Yield: 98 mg (0.21 mmol, 45%) of a yellow solid. 1H{11B} NMR analysis (%) calcd. for C21H25B11N2O2: C 55.27, H 5.52, N 6.14; found: C
(500 MHz, C6D6): δ = 9.55 (d, 1H, 3JHH = 8.5 Hz, C2aryl−H), 8.19 (d, 1H, 55.87, H 5.62, N 6.04. IR spectroscopy [ṽ]: 3074 cm-1 (Caryl−H, w),
3J
HH = 8.2 Hz, C5aryl−H), 8.18 (d, 1H, JHH = 8.1 Hz, C8aryl−H), 7.43 (dd, 1H,
3 2934 cm-1 (Calkyl−H, w), 2559 cm-1 (B−H, s), 1608 cm-1 (C=C, s), 1518 cm-
1 (C=C, s), 1484 cm-1 (C=C, s).

RESEARCH ARTICLE
4g: Yield: 136 mg (0.30 mmol, 64%) of a yellow solid. 1H{11B} NMR CamineH(CH3)2) ppm. 11B NMR (160 MHz, C6D6): δ = 37.2 (s, 1B, Bring), 1.8
(500 MHz, C6D6): δ = 9.59 (d, 1H, 3JHH = 8.2 Hz, C2aryl−H), 8.27 (d, 1H, (d, 1B, B12), −4.5 (d, 1B, B7), −7.4 (d, 2B), −8.8 (d, 4B), −9.7 (d, 2B) ppm.
HH = 8.6 Hz, C5aryl−H), 8.25 (dd, 1H, JHH = 7.8 Hz, JHH = 1.6 Hz,
13C{1H} NMR (126 MHz, C D ): δ = 156.91 (s, 1C, N−C13
aryl−N), 141.60
3J 3 4
6 6
C8aryl−H), 7.45 (ddd, 1H, 3JHH = 8.3 Hz, 4JHH = 1.3 Hz, C4aryl−H), 7.35 (ddd, (s, 1C, C6aryl), 140.92 (s, 1C, C12aryl), 139.61 (s,1C, C1aryl−B), 139.43 (s,
1H, 3JHH = 8.4 Hz, 4JHH = 1.2 Hz, C3aryl−H), 7.09 (ddd, 1H, 3JHH = 7.8 Hz, 1C, C7aryl), 133.71 (s, 1C, C2aryl), 128.99 (s, 1C, C4aryl), 128.82 (s, 1C,
HH = 1.6 Hz, C9/10/11aryl−H), 7.06 (dd, 1H, JHH = 8.2 Hz, JHH = 1.7 Hz,
4J 3 4 C9aryl), 127.66 (s, 1C, C8aryl), 127.63 (s, 1C, C5aryl), 126.97 (s, 1C, C10aryl),
C9/10/11aryl−H), 7.02 (ddd, 1H, 3JHH = 9.3 Hz, 4JHH = 1.8 Hz, 126.14 (s, 1C, C3aryl), 124.46 (s, 1C, C11aryl), 78.41 (s, 1C, Ccage−CH3),
C9/10/11aryl−H), 6.79 (s, 1H, C2/6phenyl−H), 6.63 (s, 1H, C2/6phenyl−H), 6.45 72.28 (s, 1C, Ccage−B), 53.33 (s, 1C, CamineH(CH3)2), 51.05 (s, 1C,
(s, 2H, C3+5phenyl−H), 3.52 (s, 1H, B−H), 3.43 (s, 1H, B−H), 3.21 (s, 2H, CimineH(CH3)2), 26.42 (s, 1C, CimineH(CH3)2), 24.14 (s, 1C, Ccage−CH3),
B−H), 2.96 (s, 2H, B−H), 2.79 (s, 1H, B−H), 2.58 (s, 2H, B−H), 2.43 (s, 6H, 23.82 (s, 1C, CamineH(CH3)2), 22.86 (s, 1C, CamineH(CH3)2), 20.86 (s, 1C,
N(CH3)2), 2.30 (s, 1H, B−H), 1.29 (s, 3H, CH3) ppm. 11B NMR (160 MHz, CimineH(CH3)2) ppm. HRMS (LIFDI): calcd. for 5a: m/z = 446.3896; found:
C6D6): δ = 33.0 (s, 1B, Bring), 2.2 (d, 1B), -5.2 (d, 1B), -7.6 (d, 6B), -8.9 (d, m/z = 446.3886. Elemental analysis (%) calcd. for C22H35B11N2: C 59.19,
2B) ppm. 13C{1H} NMR (126 MHz, C6D6): δ = 150.67 (s, 1C, C4phenyl), H 7.90, N 6.27; found: C 60.22, H 8.15, N 6.50. IR spectroscopy [ṽ]:
143.05 (s, 1C, C12aryl), 140.19 (s, 1C, C6aryl), 138.70 (s, 1C, C1aryl), 132.11 3048 cm-1 (Caryl−H, w), 2917 cm-1 (Calkyl−H, w), 2559 cm-1 (B−H, s),
(s, 1C, C2/6phenyl), 131.47 (s, 1C, C1phenyl), 131.28 (s, 1C, C2/6phenyl), 1662 cm-1 (C=C, s), 1434 cm-1 (C=C, s).
Accepted Manuscript
130.44 (s, 1C, C1aryl−B), 128.05 (s, 1C, C9/10/11aryl), 125.66 (s, 1C, C3aryl),
125.15 (s, 1C, C7aryl), 123.89 (s, 1C, C8aryl), 123.48 (s, 1C, C9/10/11aryl), Synthesis of 5b: 9-borafluorene 1 (150 mg, 0.47 mmol) was dissolved in
122.72 (s, 1C, C5aryl), 120.89 (s, 1C, C9/10/11aryl), 112.68 (s, 1C, 3 mL of toluene and a solution of N,N’-dicyclohexylcarbodiimide (96 mg,
C3/5phenyl), 112.03 (s, 1C, C3/5phenyl), 78.27 (s, 1C, Ccage−CH3), 75.87 (s, 0.47 mmol) in 1 mL of toluene was added slowly. The reaction mixture was
1C, Ccage−B), 39.88 (s, 2C, N(CH3)2), 25.36 (s,1C, Ccage−CH3) ppm. HRMS stirred at room temperature for 1 h before it was concentrated under
(LIFDI): calcd. for 4g: m/z = 454.3583; found: m/z = 454.3574. Elemental vacuum. The addition of hexane (3 mL) resulted in precipitation of a
analysis (%) calcd. for C23H31B11N2: C 60.79, H 6.88, N 6.16; found: C colorless solid, which was washed with hexane (5 x 1 mL) and dried in
61.47, H 6.82, N 6.23. IR spectroscopy [ṽ]: 3059 cm-1 (Caryl−H, w), vacuo. Suitable crystals for X-ray diffraction analysis were obtained by
2892 cm-1 (Calkyl−H, w), 2578 cm-1 (B−H, s), 1610 cm-1 (C=C, s), 1518 cm- slow diffusion of pentane into a saturated benzene solution of 5b. Yield:
1 (C=C, s), 1436 cm-1 (C=C, s).
173 mg (0.33 mmol, 70%) of a colorless solid. 1H{11B} NMR (500 MHz,
C6D6): δ = 7.90 (d, 1H, 3J HH = 7.9 Hz, C2aryl−H), 7.21 (d, 1H, 3JHH = 7.5 Hz,
4h: Yield: 148 mg (0.34 mmol, 71%) of a yellow solid. 1H{11B} NMR C8aryl−H), 7.18 (d, 1H, 3JHH = 7.6 Hz, C5aryl−H), 7.10 (td, 1H, 3JHH = 7.7 Hz,
(500 MHz, C6D6): δ = 9.56 (d, 1H, 3JHH = 8.2 Hz, C2aryl−H), 8.25 (d, 1H, 4J
HH = 1.3 H, C4aryl−H), 7.02 (td, 1H, JHH = 7.5 Hz, JHH = 1.5 Hz, C9aryl−H),
3 4
HH = 8.6 Hz, C5aryl−H), 8.23 (d, 1H, JHH = 8.1 Hz, C8aryl−H), 7.44 (dd, 1H, 7.00 (m, 1H, C10aryl−H), 6.98 (m, 1H, C3aryl−H), 6.90 (dm, 1H, 3JHH = 7.4 Hz,
3J 3
3
JHH = 8.1 Hz, C4aryl−H), 7.33 (ddd, 1H, 3J HH = 8.4 Hz, C3aryl−H), 7.09 (dd, C11aryl−H), 4.88 (m, 1H, C1imineH), 3.19 (s, 1H, B−H), 2.97 (m, 1H,
1H, 3JHH = 8.2 Hz, C9aryl−H), 7.04 (dd, 1H, 3JHH = 8.6 Hz, C10aryl-H), 6.82 C1amineH), 2.94 (s, 5H, B−H), 2.77 (m, 1H, , C6imineH2), 2.46 (s, 1H, B−H),
(d, 1H, 3J HH = 8.6 Hz, C11aryl−H), 6.72 (s, 1H, C2/6phenyl−H), 6.71 (s, 1H, 2.40 (s, 2H, B−H), 2.28 (s, 1H, B−H), 2.02 (d, 1H, 3J HH = 11.8 Hz, C6imineH2),
C3/5phenyl−H), 6.66 (s, 1H, C3/5phenyl−H), 6.54 (s, 1H, C2/6phenyl−H), 3.48 (s, 1.80 (m, 1H, C2imineH2), 1.72 (m, 3H, C2+5imineH2/ C2amineH2), 1.55 (m, 4H,
1H, B−H), 3.40 (s, 1H, B−H), 3.24 (s, 3H, OCH3), 3.22 (s, 2H, B−H), 2.95 C3imineH2/ C2+3amineH2), 1.29 (m, 5H, C4+5imineH2/ C5+6amineH2), 1.04 (m,
(s, 2H, B−H), 2.78 (s, 1H, B−H), 2.57 (s, 1H, B−H), 2.47 (s, 1H, B−H), 2.28 4H, C3imineH2/ C3+4+6amineH2), 0.90 (s, 3H, CH3), 0.72 (m, 2H,
(s, 1H, B−H), 1.20 (s, 3H, CH3) ppm. 11B NMR (160 MHz, C6D6): δ = 32.8 C4+5amineH2) ppm. 11B NMR (160 MHz, C6D6): δ = 37.4 (s, 1B, Bring), 1.9
(s, 1B, Bring), 2.3 (d, 1B), −5.2 (d, 1B), −7.5 (d, 6B), −9.0 (d, 2B) ppm. (d, 1B, B12), −4.5 (d, 1B, B7), −7.5 (d, 2B), −8.8 (d, 4B), −9.8 (d, 2B) ppm.
13C{1H} NMR (126 MHz, C D ): δ = 160.49 (s, 1C, C4 13C{1H} NMR (126 MHz, C D ): δ = 157.11 (s, 1C, N−C13
6 6 phenyl), 142.45 (s, 1C, 6 6 aryl−N), 141.71
C12aryl), 140.12 (s, 1C, C6aryl), 138.72 (s, 1C, C2aryl), 135.73 (s, 1C, (s, 1C, C6aryl), 141.17 (s, 1C, C12aryl), 139.64 (s,1C, C1aryl−B), 139.47 (s,
C1phenyl), 132.56 (s, 1C, C2/6phenyl), 131.90 (s, 1C, C2/6phenyl), 131.64 (s, 1C, C7aryl), 133.80 (s, 1C, C2aryl), 129.00 (s, 1C, C4aryl), 128.80 (s, 1C,
1C, C4aryl), 130.21 (s, 1C, C1aryl−B), 125.75 (s, 1C, C3aryl), 125.11 (s, 1C, C9aryl), 127.67 (s, 1C, C8aryl), 127.58 (s, 1C, C5aryl), 126.97 (s, 1C, C10aryl),
C7aryl), 123.97 (s, 1C, C8aryl), 123.62 (s, 1C, C9aryl), 122.73 (s, 1C, C5aryl), 126.13 (s, 1C, C3aryl), 124.52 (s, 1C, C11aryl), 78.48 (s, 1C, Ccage−CH3),
120.61 (s, 1C, C10aryl), 115.45 (s, 1C, C3/5phenyl), 114.22 (s, 1C, C3/5phenyl), 72.45 (s, 1C, Ccage−B), 60.99 (s, 1C, C1amineH), 59.48 (s, 1C, C1imineH),
78.32 (s, 1C, Ccage−CH3), 75.49 (s, 1C, Ccage−B), 55.08 (s, 1C, OCH3), 36.97 (s, 1C, C6imineH2), 34.15 (s, 1C, C2amineH2), 32.92 (s, 1C, C4amineH2),
25.30(s,1C, Ccage−CH3) ppm. HRMS (LIFDI): calcd. for 4h: m/z = 32.00 (s, 1C, C2imineH2), 26.52 (s, 1C, C5imineH2), 26.43 (s, 1C, C4imineH2),
441.3267; found: m/z = 441.3256. Elemental analysis (%) calcd. for 26.02 (s, 1C, C3amineH2), 25.79 (s, 1C, C6amineH2), 24.18 (s, 2C, C3imineH2/
C22H28B11NO: C 59.87, H 6.39, N 3.17; found: C 59.67, H 6.56, N 3.05. IR Ccage−CH3), 23.83 (s, 1C, C5amineH2) ppm. HRMS (LIFDI): calcd. for 5b:
spectroscopy [ṽ]: 3055 cm-1 (Caryl−H, w), 2956 cm-1 (Calkyl−H, w), 2572 cm- m/z = 526.4522; found: m/z = 526.4509. Elemental analysis (%) calcd. for
1 (B−H, s), 1606 cm-1 (C=C, s), 1507 cm-1 (C=C, s), 1434 cm-1 (C=C, s). C28H43B11N2: C 63.87, H 8.23, N 5.32; found: C 63.79, H 8.08, N 6.19. IR
spectroscopy [ṽ]: 3057 cm-1 (Caryl−H, w), 2924 cm-1 (Calkyl−H, w), 2574 cm-
1
Synthesis of 5a: 9-borafluorene 1 (150 mg, 0.47 mmol) was dissolved in (B−H, s), 1659 cm-1 (C=C, s), 1434 cm-1 (C=C, s).
3 mL of toluene and a solution of N,N’-diisopropylcarbodiimide (59 mg,
0.47 mmol) in 1 mL of toluene was added slowly. The reaction mixture was Synthesis of 6: 9-borafluorene 1 (150 mg, 0.47 mmol) was dissolved in
stirred at room temperature for 1 h before it was concentrated under 3 mL of toluene and a solution of phenyl isocyanate (56 mg, 0.47 mmol) in
vacuum. Addition of hexane (3 mL) resulted in precipitation of a colorless 2 mL of toluene was added slowly. The reaction mixture was stirred at
solid, which was washed with hexane (5 x 1 mL) and dried in vacuo. room temperature for 1 h before it was concentrated under vacuum. The
Suitable crystals for X-ray diffraction analysis were obtained by slow addition of hexane (5 mL) resulted in precipitation of a colorless solid,
diffusion of pentane into a saturated toluene solution of 5a. Yield: 187 mg which was washed with hexane (10 x 1 mL) and dried in vacuo. Yield:
(0.42 mmol, 89%) of a colorless solid. 1H{11B} NMR (500 MHz, C6D6): δ = 142 mg (0.32 mmol, 69%) of a colorless solid. 1H{11B} NMR (500 MHz,
7.88 (d, 1H, 3JHH = 7.8 Hz, C2aryl−H), 7.20 (d, 1H, 3JHH = 7.7 Hz, C8aryl−H), C6D6): δ = 7.90 (dm, 1H, C2aryl−H), 7.64 (d, 1H, 3JHH = 7.7 Hz, C11aryl−H),
7.15 (d, 1H, 3JHH = 7.8 Hz, C5aryl−H), 7.08 (dt, 1H, 3JHH = 7.6 Hz, 4JHH = 7.15 – 6.93 (m, 5H, Cphenyl−H), 7.14 (m, 1H, C4aryl−H), 7.11 (m, 2H,
1.3 Hz; C4aryl−H), 7.01 (dt, 1H, 3JHH = 7.5 Hz, 4JHH = 1.4 Hz, C9aryl−H), 6.97 C3+5aryl−H), 7.08 (m, 1H, C8aryl−H), 7.3 (m, 1H, C9aryl−H), 6.98 (m, 1H,
(dt, 1H, 3JHH = 7.5 Hz, 4JHH = 1.3 Hz, C3aryl−H), 6.95 (dt, 1H, 3JHH = 7.5 Hz, C10aryl−H), 3.08 (s, 1H, B−H), 2.83 (s, 1H, B−H), 2.78 (s, 1H, B−H), 2.73
HH = 1.3 Hz, C10aryl−H), 6.84 (dm, 1H, JHH = 7.6 Hz, C11aryl−H), 5.19
4J 3 (s, 1H, B−H), 2.56 (s, 1H, B−H), 2.47 (s, 1H, B−H), 2.26 (s, 2H, B−H), 2.24
(sept, 1H, CimineH(CH3)2), 3.18 (s, 1H, B−H), 3.13 (sept, 1H, CamineH(CH3)2), (s, 1H, B−H), 1.17 (s, 1H, B−H), 0.99 (s, 3H, CH3) ppm. 11B NMR (160 MHz,
2.99 (s, 1H, B−H), 2.96 (s, 2H, B−H), 2.93 (s, 2H, B−H), 2.44 (s, 1H, B−H), C6D6): δ = 50.0 (s, 1B, Bring), 2.4 (d, 1B, B12), −4.4 (d, 1B, B7), −7.6 (d,
2.40 (s, 2H, B−H), 2.27 (s, 1H, B−H), 1.63 (d, 3H, 3JHH = 6.6 Hz, 2B), −8.6 (d, 4B), −9.1 (d, 2B) ppm. 13C{1H} NMR (126 MHz, C6D6): δ =
CimineH(CH3)2), 1.10 (d, 3H, 3JHH = 6.6 Hz, CimineH(CH3)2), 0.99 (d, 3H, 3J HH 174.76 (s, 1C, C13aryl−O), 140.71 (s, 1C, C1aryl−B), 140.30 (s, 1C, C6aryl),
= 6.2 Hz, CamineH(CH3)2), 0.87 (s, 3H, CH3), 0.37 (d, 3H, 3JHH = 6.2 Hz, 140.16 (s,1C, C1phenyl), 138.42 (s, 1C, C7aryl), 138.34 (s, 1C, C11aryl),
9

RESEARCH ARTICLE
131.25 (s, 2C, C2+9aryl), 131.09 (s, 1C, C4aryl), 130.74 (s, 2C, 26.10 (s, 1C, Ccage−CH3), 24.83 (s, 1C, C6mesityl−CH3), 22.58 (s, 1C,
C2+6/3+5phenyl), 129.93 (s, 1C, C11aryl), 129.73 (s, 2C, C2+6/3+5phenyl), C4mesityl−CH3), 21.13 (s, 1C, C2mesityl−CH3) ppm. HRMS (LIFDI): calcd. for
129.23 (s, 1C, C4phenyl), 128.90 (s, 1C, C3/5aryl), 128.34 (s, 1C, C10aryl), 8: m/z = 521.4428; found: m/z = 521.4410; calcd. for [8–isobutylene
128.14 (s, 1C, C8aryl), 127.22 (s, 1C, C3/5aryl), 78.94 (s, 1C, Ccage−CH3), (C4H8)]: m/z = 465.3802; found: m/z = 465.3788. Elemental analysis (%)
72.27 (s, 1C, Ccage−B), 24.12 (s, 1C, Ccage−CH3) ppm. HRMS (LIFDI): calcd. calcd. for C28H41B12N: C 64.51, H 7.93, N 2.69; found: C 64.92, H 8.15, N
for 6: m/z = 439.3111; found: m/z = 439.3101. Elemental analysis (%) 2.65. IR spectroscopy [ṽ]: 3051 cm-1 (Caryl−H, w), 2913 cm-1 (Calkyl−H, m),
calcd. for C22H26B11NO: C 60.14, H 5.96, N 3.19; found: C 60.38, H 6.03, 2576 cm-1 (B−H, s), 1604 cm-1 (C=C, w), 1470 cm-1 (C=C, w), 1428 cm-1
N 3.10. IR spectroscopy [ṽ]: 3055 cm-1 (Caryl−H, w), 2576 cm-1 (B−H, s), (C=C, s).
1702 cm-1 (O=C, s), 1593 cm-1 (C=C, m), 1432 cm-1 (C=C, m).
Synthesis of 9: 9-borafluorene 1 (150 mg, 0.47 mmol) was dissolved in
Synthesis of 7: 9-borafluorene 1 (150 mg, 0.47 mmol) was dissolved in 3 mL of toluene and 1-adamantyl phosphaalkyne (84 mg, 0.47 mmol) in
3 mL of toluene and a solution of p-chlorophenyl thioisocyanate (80 mg, 1 mL of toluene was added slowly. The reaction mixture was stirred at
0.47 mmol) in 2 mL toluene was added slowly. The reaction mixture was room temperature for 30 min before it was concentrated under vacuum.
stirred at room temperature for 1 h before it was concentrated under The addition of hexane (5 mL) resulted in precipitation of a yellow solid,
vacuum. The addition of pentane (5 mL) resulted in precipitation of a pink which was washed with hexane (10 x 1 mL) and dried in vacuo. Suitable
Accepted Manuscript
solid. The solid was washed with pentane (10 x 1 mL) and dried in vacuo. crystals for X-ray diffraction analysis were obtained by diffusion of pentane
X-ray diffraction analysis were obtained by slow evaporation of a saturated into a saturated benzene solution of 9. Yield: 113 mg (0.23 mmol, 48%) of
solution of 7 in toluene. Yield: 214 mg (0.44 mmol, 93%) of a pink solid. a yellow solid. 1H{11B} NMR (500 MHz, C6D6): δ = 7.60 (m, 1H, C11aryl−H),
1H{11B} NMR (500 MHz, CD Cl ): δ = 7.91 (d, 1H, 3J
2 2 HH = 7.7 Hz, C2aryl−H), 7.33 (m, 1H, C5aryl−H), 7.19 (m, 1H, C8aryl−H), 7.14 (m, 1H, C2aryl−H), 7.07
7.74 (d, 1H, 3JHH = 7.9 Hz, C11aryl−H), 7.65 (td, 1H, 3JHH = 7.6 Hz, 4JHH = (m, 2H, C3+4aryl−H), 6.95 (m, 2H, C9+10aryl−H), 3.19 (s, 1H, B−H), 2.91 (s,
1.3 H, C4aryl−H), 7.61 (tm, 1H, 3JHH = 7.9 Hz, C5aryl−H), 7.55 (td, 1H, 3J HH 2H, B−H), 2.81 (s, 1H, B−H), 2.74 (s, 1H, B−H), 2.67 (s, 1H, B−H), 2.35 (s,
= 7.4 Hz, 4J HH = 1.4 H, C3aryl−H), 7.50 (m, 3H, C9aryl−H/C3+5phenyl−H), 7.45 1H, B−H), 2.28 (s, 1H, CH2/CHadamantyl), 2.25 (s, 2H, CH2/CHadamantyl), 2.22
(dd, 1H, 3JHH = 7.9 Hz, 4JHH = 1.4 H, C8aryl−H), 7.40 (td, 1H, 3JHH = 7.6 Hz, (s, 2H, B−H), 2.03 (s, 2H, CH2/CHadamantyl), 2.00 (s, 1H, CH2/CHadamantyl),
HH = 1.4 H, C10aryl−H), 7.13 (d, 2H, JHH = 7.0 Hz, C2+6phenyl−H), 2.43 (s,
4J 3 1.86 (s, 3H, CH2/CHadamantyl), 1.62 (s, 1H, B−H), 1.56 (m, 6H,
1H, B−H), 2.35 (s, 1H, B−H), 2.33 (s, 1H, B−H), 2.18 (s, 2H, B−H), 2.05 (s, CH2/CHadamantyl), 1.08 (s, 3H, CH3) ppm. 11B NMR (160 MHz, C6D6): δ =
1H, B−H), 2.01 (s, 1H, B−H), 1.97 (s, 1H, B−H), 1.96 (s, 1H, B−H), (s, 3H, 73.2 (s, 1B, Bring), 3.3 (d, 1B, B12), −4.6 (d, 1B, B7), −7.7 (d, 4B), −8.3 (d,
CH3), 1.30 (s, 1H, B−H) ppm. 11B NMR (160 MHz, CD2Cl2): δ = 51.2 (s, 1B, 2B), −9.4 (d, 2B) ppm. 13C{1H} NMR (126 MHz, C6D6): δ = 148.78 (s, 1C,
Bring), 2.0 (d, 1B, B12), −5.2 (d, 1B, B7), −7.9 (d, 2B), −9.0 (d, 4B), −9.9 (d, C1aryl−B), 143.16 (s, 1C, C7aryl), 138.45 (s, 1C, C6aryl), 137.81 (d, 1C,
2B) ppm. 13C{1H} NMR (126 MHz, CD2Cl2): δ = 216.57 (s, 1C, C13aryl−S), C11aryl), 136.54 (s, 1C, C12aryl−P), 130.73 (s, 1C, C8aryl), 129.84 (s, 1C,
145.85 (s, 1C, C11aryl), 142.05 (s, 1C, C1phenyl), 141.68 (s,1C, C1aryl−B), C9aryl), 128.21 (s, 1C, C3/4aryl), 128.11 (s, 1C, C5aryl), 127.09 (s, 1C,
140.78 (s, 1C, C6aryl), 135.55 (s, 1C, C4phenyl−Cl), 135.36 (s, 1C, C7aryl), B−C13alkenyl−P), 126.99 (s, 1C, C10aryl), 126.43 (s, 1C, C3/4aryl), 123.29 (s,
131.74 (s, 1C, C4aryl), 131.72 (s, 2C, C2+6phenyl), 131.39 (s, 1C, C11aryl), 1C, C2aryl), 78.20 (s, 1C, Ccage−CH3), 74.04 (s, 1C, Ccage−B), 48.11 (d, 1C,
130.68 (s, 1C, C9aryl), 130.31 (s, 2C, C2+6phenyl), 130.27 (s, 1C, C2aryl), C1adamantyl), 46.86 (d, 3C, Cadamantyl), 36.53 (s, 3C, Cadamantyl), 29.74 (s, 3C,
128.28 (s, 1C, C5aryl), 128.00 (s, 1C, C10aryl), 127.93 (s, 1C, C8aryl), 127.19 Cadamantyl), 25.10 (s, 1C, Ccage−CH3) ppm. 31P NMR (202.5 MHz, C6D6):
(s, 1C, C3aryl), 79.11 (s, 1C, Ccage−CH3), 71.61 (s, 1C, Ccage−B), 24.22 (s, δ (ppm) = 205.26 ppm. HRMS (LIFDI): calcd. for 9: m/z = 498.3651; found:
1C, Ccage−CH3) ppm. HRMS (LIFDI): calcd. for 7: m/z = 489.2492; found: m/z = 498.3632. Elemental analysis (%) calcd. for C26H36B11P: C 62.65, H
m/z = 489.2473. Elemental analysis (%) calcd. for C22H25B11ClNS: C 55.94, 7.28; found: C 63.62, H 7.56. IR spectroscopy [ṽ]: 3051 cm-1 (Caryl−H, w),
H 5.14, N 2.86, S 6.54; found: C 55.73, H 5.76, N 2.60, S 5.57. IR 2913 cm-1 (Calkyl−H, s), 2570 cm-1 (B−H, s), 1593 cm-1 (C=C, w), 1425 cm-
spectroscopy [ṽ]: 3060 cm-1 (Caryl−H, w), 2574 cm-1 (B−H, s), 1591 cm-1 1 (C=C, m).
(C=C, w), 1483 cm-1 (C=C, m), 1430 cm-1 (C=C, m).
Synthesis of 10a: 9-borafluorene 1 (150 mg, 0.47 mmol) was dissolved in
Synthesis of 8: 9-borafluorene 1 (150 mg, 0.47 mmol) was dissolved in 3 mL of toluene and a solution of benzaldehyde (50 mg, 0.47 mmol) in
3 mL of toluene, cooled to −78 °C and a solution of (tert- 1 mL of toluene was added slowly. The reaction mixture was stirred at
butylimino)mesitylborane (101 mg, 0.50 mmol, 1 M in hexane, 0.5 mL) in room temperature for 1 h before it was concentrated under vacuum. The
2 mL of toluene was added slowly. The reaction mixture was stirred at addition of pentane (5 mL) resulted in precipitation of a colorless solid,
−78 °C for 3 h and then warmed to room temperature. The reaction mixture which was washed with pentane (5 x 1 mL) and dried in vacuo. Suitable
was concentrated under vacuum. After addition of pentane (5 mL), a crystals for X-ray diffraction analysis were obtained by slow evaporation of
colorless solid precipitated, which was washed with pentane (5 x 1 mL) a saturated toluene solution of 10a. Yield: 131 mg (0.31 mmol, 65%) of a
and dried in vacuo. Suitable crystals for X-ray diffraction analysis were colorless solid. 1H{11B} NMR (500 MHz, C6D6): δ = 7.96 (dm, 1H, 3JHH =
obtained by slow diffusion of pentane into a saturated solution of 8 in 7.6 Hz, C2aryl−H), 7.35 (d, 1H, 3JHH = 7.6 Hz, C5aryl−H), 7.27 (m, 1H,
benzene. Yield: 156 mg (0.30 mmol, 64%) of a colorless solid. 1H{11B} C4aryl−H), 7.25 (m, 1H, C8aryl−H), 7.22 (m, 2H, C2+6phenyl−H), 7.13 (m, 3H,
NMR (500 MHz, C6D6): δ = 7.44 (d, 1H, 3JHH = 7.8 Hz, C2aryl−H), 7.40 (d, C3+4+5phenyl−H), 7.11 (m, 1H, C3aryl−H), 7.02 (td, 1H, 3JHH = 7.5 Hz, 4JHH =
1H, 3JHH = 7.8 Hz C8aryl−H), 7.14 (m, 1H, C9aryl−H), 7.11 (m, 1H, C5aryl−H), 1.3 Hz, C9aryl−H), 6.83 (dt, 1H, 3JHH = 7.6 Hz, 4JHH = 1.3 Hz, C10aryl−H),
7.08 (m, 1H, C11aryl−H), 7.01 (m, 2H, C4+10aryl−H), 6.90 (td, 2H, 3JHH = 6.74 (dm, 1H, 3JHH = 7.8 Hz, C11aryl−H), 5.80 (s, 1H, O−C13alkylHPh), 3.15
7.5 Hz, 4JHH = 1.3 Hz, C3aryl−H), 6.82 (s, 1H, C5mesityl−H), 6.50 (s, 1H, (s, 1H, B−H), 2.94 (s, 1H, B−H), 2.91 (s, 1H, B−H), 2.86 (s, 1H, B−H), 2.81
C3mesityl−H), 3.24 (s, 1H, B−H), 3.00 (s, 1H, B−H), 2.95 (s, 1H, B−H), 2.89 (s, 1H, B−H), 2,78 (s, 1H, B−H), 2.59 (s, 1H, B−H), 2.50 (s, 2H, B−H), 2.42
(s, 2H, B−H), 2.73 (s, 1H, B−H), 2.70 (s, 3H, C6mesityl−CH3), 2.57 (s, 1H, (s, 1H, B−H), 1.25 (s, 3H, CH3) ppm. 11B NMR (160 MHz, C6D6): δ = 41.7
B−H), 2.41 (s, 1H, B−H), 2.21 (s, 1H, B−H), 2.09 (s, 3H, C2mesityl−CH3), (s, 1B, Bring), 1.3 (d, 1B, B12), −4.7 (d, 1B, B7), −7.5 (d, 1B), −7.9 (d, 2B),
1.61 (s, 3H, C4mesityl−CH3), 1.29 (s, 9H, NC(CH3)3), 1.22 (s, 1H, B−H), 1.07 −9.1 (d, 4B), −10.3 (d, 1B) ppm. 13C{1H} NMR (126 MHz, C6D6): δ = 144.47
(s, 3H, Ccage−CH3) ppm. 11B NMR (160 MHz, C6D6): δ = 65.3 (s, 1B, Bring), (s, 1C, C6aryl), 142.10 (s, 1C, C12aryl), 140.54 (s, 1C, C7aryl), 137.94 (s,1C,
39.5 (s, 1B, Bmesityl), 3.4 (d, 1B, B12), −4.9 (d, 1B, B7), −7.7 (d, 2B), −8.4 C1phenyl), 134.56 (s, 1C, C2aryl), 133.83 (s, 1C, C1aryl−B), 131.93 (s, 1C,
(d, 4B), −9.8 (d, 2B) ppm. 13C{1H} NMR (126 MHz, C6D6): δ = 146.76 (s, C4aryl), 129.70 (s, 1C, C8aryl), 129.43 (s, 1C, C5aryl), 129.28 (s, 1C, C9aryl),
1C, C12aryl−B), 145.12 (s, 1C, C6aryl), 142.03 (s, 1C, C7aryl), 141.55 (s,1C, 128.78 (s, 2C, C3+5phenyl), 128.36 (s, 1C, C4phenyl), 127.85 (s, 1C, C10aryl),
C1mesityl−B), 139.29 (s, 1C, C2mesityl), 138.03 (s, 1C, C1aryl−B), 137.93 (s, 127.30 (s, 2C, C2+6phenyl), 126.96 (s, 1C, C11aryl), 126.78 (s, 1C, C3aryl),
1C, C2aryl), 137.56 (s, 1C, C6mesityl), 137.18 (s, 1C, C4mesityl), 130.08 (s, 1C, 79.19 (s, 1C, C13alkyl−O), 76.48 (s, 1C, Ccage−CH3), 71.57 (s, 1C, Ccage−B),
C4aryl), 129.31 (s, 1C, C9aryl), 128.39 (s, 1C, C3mesityl), 128.35 (s, 1C, C5aryl), 24.63 (s, 1C, Ccage−CH3) ppm. HRMS (LIFDI): calcd. for 10a: m/z =
128.14 (s, 1C, C5mesityl), 127.71 (s, 1C, C8aryl), 127.43 (s, 1C, C3aryl), 426.3158; found: m/z = 426.3146. Elemental analysis (%) calcd. for
126.59 (s, 1C, C11aryl), 125.94 (s, 1C, C10aryl), 78.53 (s, 1C, Ccage−CH3), C28H311B11O: C 66.93, H 6.22; found: C 67.11, H 6.37. IR spectroscopy [ṽ]:
75.81 (s, 1C, Ccage−B), 59.11 (s, 1C, NC(CH3)3), 32.36 (s; 3C, NC(CH3)3),,
10

RESEARCH ARTICLE
3059 cm-1 (Caryl−H, w), 2892 cm-1 (Calkyl−H, m), 2566 cm-1 (B−H, s), Addition of hexane (10 mL) resulted in precipitation of a yellow solid, which
1595 cm-1 (C=C, m), 1479 cm-1 (C=C, w), 1434 cm-1 (C=C, s). was washed with hexane (5 x 1 mL) and dried in vacuo. Suitable crystals
for X-ray diffraction analysis were obtained by slow diffusion of hexane into
Synthesis of adduct 10b-int: 9-borafluorene 1 (150 mg, 0.47 mmol) was a saturated solution of 11 in benzene. Yield: 224 mg (0.43 mmol, 92%) of
dissolved in 3 mL of toluene and a solution of benzophenone (87 mg, a yellow solid. 1H{11B} NMR (500 MHz, C6D6): δ = 7.36 (d, 1H, 3JHH =
0.47 mmol) in 1 mL of toluene was added slowly. The reaction mixture was 7.4 Hz, C2aryl−H), 7.23 (td, 1H, 3JHH = 7.6 Hz, 4JHH = 1.4 Hz, C4aryl−H), 7.14
stirred at room temperature for 1 h. Addition of hexane (3 mL) resulted in (td, 2H, 3J HH = 7.5 Hz, 4JHH = 1.2 Hz, C3aryl−H), 7.07 (dm, 1H, 3JHH = 7.6 Hz,
precipitation of a colorless solid, which was washed with hexane (5 x 1 mL) C5aryl−H), 6.97 (m, 3H, C9/11aryl−H/ C8/10aryl−H/ C2+6/3+5phenyl-H), 6.89
and dried in vacuo. Suitable crystals for X-ray diffraction analysis were (m, 5H, C9/11aryl−H/ C2+6/3+5phenyl−H), 6.77 (m, 6H, C4/2+6/3+5phenyl−H),
obtained by cooling a saturated toluene solution of 10b-Int to −30 °C. 4.35 (s, 1H, N−C13alkylHPh), 3.14 (s, 1H, B−H), 2.88 (s, 1H, B−H), 2.84 (s,
Yield: 207 mg (0.41 mmol, 88%) of a colorless solid. 1H{11B} NMR 1H, B−H), 2.78 (s, 1H, B−H), 2.62 (s, 2H, B−H), 2.48 (s, 1H, B−H), 2.42 (s,
(500 MHz, C6D6): δ = 7.52 (dm, 2H, 3JHH = 7.2 Hz, C2+11aryl−H), 7.07 (m, 1H, B−H), 2.33 (s, 1H, B−H), 2.10 (s, 1H, B−H), 1.34 (s, 3H, CH3) ppm.
2H, C2+6phenyl−H), 7.06 (m, 2H, C5+8aryl−H), 7.02 (m, 2H, C4+9aryl−H),
11
B NMR (160 MHz, C6D6): δ = 46.2 (s, 1B, Bring), 1.8 (d, 1B, B12), −5.0 (d,
6.91 (td, 2H, 3JHH = 7.2 Hz, 4JHH = 1.4 Hz, C3+10aryl−H), 6.88 (tm, 2H, 1B, B7), −7.4 (d, 1B), −7.5 (d, 1B), −8.7 (d, 2B), −9.9 (d, 4B) ppm. 13C{1H}
3J
HH = 7.5 Hz, C4phenyl−H), 6.67 (tm, 2H, JHH = 7.7 Hz, C3+5phenyl−H), 3.28
3 NMR (126 MHz, C6D6): δ = 149.33 (s, 1C, C1phenyl−N), 144.73 (s, 1C,
Accepted Manuscript
(s, 1H, B−H), 3.25 (s, 1H, B−H), 3.21 (s, 2H, B−H), 3.07 (s, 4H, B−H), 2.58 C6aryl), 140.76 (s, 1C, C7aryl), 140.43 (s,1C, C1phenyl), 139.20 (s, 1C, C12aryl),
(s, 2H, B−H), 1.15 (s, 3H, Ccage−CH3) ppm. 11B NMR (160 MHz, C6D6): 137.89 (s, 1C, C1aryl−B), 134.30 (s, 1C, C8/10aryl), 130.18 (s, 1C, C9/11aryl),
δ = 19.5 (s, 1B, Bring), −0.4 (d, 1B, B12), −4.3 (d, 1B, B7), −8.0 (d, 2B), −8.8 129.84 (s, 1C, C4aryl), 129.20 (s, 1C, C2aryl), 128.90 (s, 2C, C2+6/3+5phenyl),
(d, 4B), −9.6 (d, 2B) ppm. 13C{1H} NMR (126 MHz, C6D6): δ = 205.7 (s, 1C, 128.78 (s, 1C, C5aryl), 128.57 (s, 2C, C2+6/3+5phenyl), 128.46 (s, 1C,
O−C), 150.9 (s, 2C, C6+7aryl), 149.0 (s, 2C, C1+12aryl−B), 134.6 (s, 2C, C8/10aryl), 128.12 (s, 3C, C9/11aryl/C2+6/3+5phenyl), 127.81 (s, 1C, C4phenyl),
C1phenyl), 134.2 (s, 2C, C4phenyl), 133.9 (s, 2C, C2+11aryl), 131.0 (s, 4C, 126.69 (s, 1C, C3aryl), 126.44 (s, 1C, C4phenyl), 122.38 (s, 2C,
C2+6phenyl), 129.9 (s, 2C, C4+9aryl), 128.0 (s, 4C, C3+5phenyl), 127.1 (s, 2C, C2+6/3+5phenyl), 81.25 (s, 1C, N−C13alkyHPh), 76.63 (s, 1C, Ccage−CH3),
C3+10aryl), 119.7 (s, 2C, C5+8aryl), 78.3 (s, 1C, Ccage−B), 75.7 (s, 1C, 69.69 (s, 1C, Ccage−B), 25.16 (s, 1C, Ccage−CH3) ppm. HRMS (LIFDI): calcd.
Ccage−CH3), 23.4 (s, 1C, Ccage−CH3) ppm. HRMS (LIFDI): calcd. for 10b- for 11: m/z = 517.3580; found: m/z = 517.3562. Elemental analysis (%)
Int: m/z = 502.3471; found: m/z = 502.3457. Elemental analysis (%) calcd. calcd. for C28H32B11NO: C 64.99, H 6.23, N 2.71; found: C 65.19, H 6.33,
for C28H31B11O: C 66.93, H 6.22; found: C 66.72, H 6.35. IR spectroscopy N 2.59. IR spectroscopy [ṽ]: 3061 cm-1 (Caryl−H, w), 2879 cm-1 (Calkyl−H, m),
[ṽ]: 3048 cm−1 (CAryl−H, w), 2937 cm−1 (CAlkyl−H, w), 2559 cm−1 (B−H, s), 2582 cm-1 (B−H, s), 1597 cm-1 (C=C, m), 1490 cm-1 (C=C, s), 1432 cm-1
1801 cm−1 (C=O, w), 1595 cm−1 (C=C, w), 1531 cm−1 (C=C, m), 1449 cm−1 (C=C, s).
(C=C, m). Annotation: In solution, there is a reversible equilibrium between
borafluorene 1, free benzophenone, and adduct 10b-Int. Deposition Numbers: 2236769-2236789, contain the supplementary
crystallographic data. These data are provided free of charge by the joint
Synthesis of 10b: 9-borafluorene 1 (150 mg, 0.47 mmol) was dissolved Cambridge Crystallographic Data Centre and Fachinformationszentrum
in 3 mL of toluene and a solution of benzophenone (87 mg, 0.47 mmol) in Karlsruhe Access Structures service.
1 mL of toluene was added slowly. The reaction mixture was stirred at
room temperature for 1 h and another 16 h at 60 °C. After cooling the Supporting Information: NMR and IR spectra, X-ray structures and
solution to room temperature, it was concentrated under vacuum. Addition crystallographic data.
of pentane (5 mL) resulted in precipitation of a colorless solid, which was
washed with pentane (5 x 1 mL) and dried in vacuo. Suitable crystals for
X-ray diffraction analysis were obtained by slow diffusion of pentane into
a saturated benzene solution of 10b. Yield: 83 mg (0.17 mmol, 35%) of a Acknowledgements
colorless solid. 1H{11B} NMR (500 MHz, C6D6): δ = 8.52 (d, 1H, 3JHH =
8.1 Hz, Cphenyl−H), 7.62 (d, 1H, 3JHH = 7.8 Hz, C2aryl−H), 7.38 (m, 1H, We thank the Julius-Maximilians-Universität Würzburg for
Cphenyl−H), 7.28 (d, 1H, 3JHH = 7.7 Hz, C8aryl−H), 7.05 (m, 4H, financial support of this work.
C5+8aryl−H/Cphenyl−H), 6.90 (m, 4H, C4+10+11aryl−H/Cphenyl−H), 6.73 (m,
2H, C3aryl−H/Cphenyl−H), 6.59 (m, 4H, Cphenyl−H), 3.18 (s, 1H, B−H), 3.00 (s,
1H, B−H), 2.96 (s, 3H, B−H), 2.92 (s, 1H, B−H), 2.72 (s, 1H, B−H), 2.69 (s,
1H, B−H), 2.53 (s, 1H, B−H), 2.44 (s, 1H, B−H), 1.28 (s,3H, CH3) ppm. 11B Conflict of Interest
NMR (160 MHz, C6D6): δ = 41.8 (s, 1B, Bring), 1.2 (d, 1B, B12), −4.6 (d, 1B,
B7), −7.4 (d, 1B), −8.0 (d, 4B), −9.2 (d, 2B), −10.3 (d, 1B) ppm. 13C{1H} The authors declare no conflict of interest.
NMR (126 MHz, C6D6): δ = 145.93 (s, 1C, C6aryl), 144.87 (s, 1C, C1phenyl),
144.72 (s, 1C, C12aryl), 143.59 (s,1C, C1phenyl), 140.69 (s, 1C, C7aryl),
134.77 (s, 1C, C1aryl−B), 134.05 (s, 1C, C2aryl), 131.38 (s, 2C, C4+8aryl),
130.11 (s, 1C, C11aryl), 129.69 (s, 1C, Cphenyl), 129.35 (s, 1C, C9aryl), Data Availability Statement
129.19 (s, 1C, C5aryl), 128.95 (s, 1C, Cphenyl), 128.85 (s, 1C, Cphenyl), 127.97
(s, 1C, Cphenyl), 127.77 (s, 1C, Cphenyl), 127.44 (s, 2C, C10Aryl/CPhenyl), The data that support the findings of this study are available in the
127.27 (s, 2C, C9aryl/Cphenyl), 126.93 (s, 1C, Cphenyl), 126.05 (s, 1C, C3aryl), supplementary material of this article.
90.08 (s, 1C, C13alkyl−O), 76.21 (s, 1C, Ccage−CH3), 72.63 (s, 1C, Ccage−B),
24.42 (s, 1C, Ccage−CH3) ppm. HRMS (LIFDI): calcd. for 10b: m/z =
Keywords: ring expansion • insertion • boroles • carboranes •
502.3471; found: m/z = 502.3459. Elemental analysis (%) calcd. for
C22H27B11O: C 61.98, H 6.38; found: C 62.13, H 6.36. IR spectroscopy [ṽ]: medium-ring compounds
3055 cm-1 (Caryl−H, w), 2922 cm-1 (Calkyl−H, m), 2568 cm-1 (B−H, s),
1660 cm-1 (C=C, s), 1592 cm-1 (C=C, m), 1475 cm-1 (C=C, m), 1430 cm-1 [1] J. J. Eisch, N. K. Hota, S. Kozima, J. Am. Chem. Soc. 1969, 91, 4575-
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RESEARCH ARTICLE
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Accepted Manuscript
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12

RESEARCH ARTICLE
Entry for the Table of Contents
Accepted Manuscript
Ring expansion of a carboranyl-substituted 9-borafluorene with unsaturated substrates provides easy access to a range of
boraheterocyclic products containing six-, seven-, and eight-membered rings. Compared to known aryl- and halogen-substituted
borafluorene derivatives, the study shows that the electron-withdrawing carboranyl substituent leads to more facile and more
selective insertion reactions.
Institute and/or researcher Twitter usernames:
@Uni_WUE
@LabBraunschweig
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Chemistry A European J - 2023 - Bischof - Construction of A Diverse Range of Boron Heterocycles Via Ring Expansion of A

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15213765, ja, Downloaded from https://chemistry-europe.onlinelibrary.wiley.com/doi/10.1002/chem.202300210 by Nanyang Technological University, Wiley Online Library on [20/02/2023].

Authors: Tobias Bischof, Lukas Beßler, Ivo Krummenacher, Leon

To be cited as: Chem. Eur. J. 2023, e202300210

Link to VoR: https://doi.org/10.1002/chem.202300210

By using a diyne, we intended to install a peripheral alkyne

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Scheme 2. Synthesis and isolated yields of the B,N-phenanthrene derivatives

Figure 4. Single carbon insertion into 9-borafluorene 1 to produce 3a and its

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In summary, 9-carboranyl-9-borafluorene is shown to react with

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