pubs.acs.

org/acscatalysis Research Article

Cyclometalated Chiral-at-Ruthenium Catalyst for Enantioselective

Ring-Closing C(sp3)−H Carbene Insertion to Access Chiral
Flavanones
Feng Han, Peter H. Choi, Chen-Xi Ye, Yvonne Grell, Xiulan Xie, Sergei I. Ivlev, Shuming Chen,*
and Eric Meggers*
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ABSTRACT: A cyclometalated ruthenium complex with exclu-

sively metal-centered chirality catalyzes the conversion of
diazoketones to chiral flavanones with up to 99% yield and with
up to 96% ee. A competing oxygen attack pathway involving the
formation and [1,2]-shift (Stevens rearrangement) of an oxonium
ylide intermediate was successfully suppressed in favor of a
catalytic enantioselective ring-closing C(sp3)−H carbene insertion.
Density functional theory calculations provide a rationale for the
observed C−H insertion over the undesirable C−O formation
pathway. The method provides access to a variety of chiral
flavanones which are considered privileged scaffolds with diverse
biological activities.
KEYWORDS: asymmetric catalysis, cyclometalation, chiral-at-metal, stereogenic metal, ruthenium, carbene insertion, flavanones

■ INTRODUCTION
Chiral transition metal complexes are indispensable work-
(NHC)6 or remote NHC (rNHC)7 ligand (Figure 1a). The
incorporation of stronger σ-donating ligands, such as cyclo-
horses in asymmetric catalysis and are typically synthesized by metalating ligands featuring a metal-carbon σ bond,8 would
combining metal salts or organometallic precursors with increase the electron density at the ruthenium center and
carefully tailored chiral ligands.1 Recently, an alternative to potentially lead to chiral-at-ruthenium catalysts with distinct
the well-established metal-plus-chiral-ligand design has catalytic properties. However, in contrast to the noble metals
emerged in which chiral transition metal catalysts consist of rhodium and iridium, cyclometallation at ruthenium often
exclusively achiral ligands.2,3 This chiral-at-metal approach leads to rather unstable complexes, which explains the limited
exploits the metal-centered chirality4 that arises from the number of reported chiral cycloruthenated catalysts.9,10
Flavanones are plant metabolites with a wide variety of
assembly of achiral ligands around a metal atom. The standard
chiral-at-metal catalyst design developed in our laboratory is biological activities ranging from anticancer to antibacterial
properties.11 The flavanone structure consists of a benzodihy-
based on an octahedral coordination sphere consisting of two
dropyran-4-one core with an aryl moiety and an accompanying
configurationally inert bidentate ligands and two labile
stereocenter at the C2-position. Nature employs the enzyme
monodentate ligands.5 The cis-coordinated bidentate ligands
chalcone isomerase to set up the pyrane ring and install the
provide a helical topology, thereby creating either a Λ (left-
stereocenter, utilizing an intramolecular oxa-Michael addition
handed helix) or Δ (right-handed helix) absolute configuration
of 2′-hydroxychalcones.12 To access non-racemic flavanone
at the central metal. The configurational stability of the
derivatives with new or improved biological properties, a
bidentate ligands, which is essential for successful chirality
number of asymmetric methods have been developed,
transfer, is achieved by exploiting a combination of the chelate
including resolution methods, asymmetric reductions of
effect and a large ligand field resulting from the strong σ-
donating and π-accepting properties of the coordinating
bidentate ligands. At the same time, at least one monodentate Received: May 17, 2022
ligand is positioned trans to a strong σ-donating ligand in order Revised: July 14, 2022
to increase the lability of the monodentate ligand, thereby Published: August 5, 2022
contributing to the overall reactivity of the catalyst. In our
previously designed chiral-at-ruthenium catalysts, the strong σ-
donor ligand was either a chelating N-heterocyclic carbene

© 2022 American Chemical Society https://doi.org/10.1021/acscatal.2c02423

10304 ACS Catal. 2022, 12, 10304−10312
ACS Catalysis pubs.acs.org/acscatalysis
Figure 1. Design of chiral-at-ruthenium catalysts and application to
the synthesis of chiral flavanones. (a) Incorporation of σ-donor
ligands into chiral-at-ruthenium catalysts. (b) Synthesis of non-
racemic flavanones: state-of-the-art and this study. (c) Catalyst-
controlled reaction of diazoketones with [1,2]-shift of intermediate
oxonium ylide. (d) Cycloruthenated catalyst for ring-closing C(sp3)−
H insertion to access chiral flavanones.
flavones, conjugate additions, biomimetic oxa-Michael reac-
tions, Mitsunobu-type cyclizations, and tandem reactions of
chromone derivatives (Figure 1b).13,14 However, all of these
reported methods have limitations that are defined by the
structural and electronic requirements for the employed
substrate class. Therefore, new methods for the synthesis of
enantioenriched flavanones for medicinal investigations are
highly desirable.
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Research Article
The insertion of metal carbenoids into C(sp3)−H bonds is
an important tool for the catalytic asymmetric generation of
stereogenic centers and has been applied to access a variety of
cyclic structures, including β- and γ-lactones and lactams,
cyclopentanones, and dihydrobenzofurans, among others.15
However, the catalytic enantioselective synthesis of chiral
flavanones by ring-closing carbene C−H insertion is problem-
atic due to a competing oxygen attack pathway involving the
formation and [1,2]-shift (Stevens rearrangement) of an
oxonium ylide intermediate, affording benzofuranones instead
of the desired chromanones (Figure 1c).16−18 α-Unsubstituted
diazoketones, for instance, failed to provide the C−H carbene
insertion products with a number of tested copper and
dirhodium catalysts.16−18
Herein, we introduce a cyclometalated chiral-at-ruthenium
complex capable of catalyzing the ring-closing C(sp3)−H
carbene insertion of diazoketones, furnishing chiral flavanones
in high yields (up to 99%) and with high enantioselectivities
(up to 96% ee) (Figure 1d). This method provides a new
strategy for the catalytic asymmetric synthesis of chiral
flavanones.
■ RESULTS AND DISCUSSION
Initial Optimization. We commenced our study by
investigating the ring-closing reaction of diazoketone 1. As
expected, with the dirhodium catalyst [Rh2(OAc)4] (2.0 mol
%) in dichloromethane at room temperature, the Stevens
rearrangement product 2 was obtained as the main product in
69% yield without any traces of flavanone 3, consistent with a
report by West almost 30 years ago (Table 1, entry 1).17
However, when we used the previously developed chiral-at-
ruthenium catalyst Λ-Ru16 instead, flavanone (S)-3 was
formed in 32% yield and with 38% ee (entry 2). Other chiral
ruthenium catalysts developed in our laboratory provided
inferior results. The ruthenium catalyst Λ-Ru27 provided
neither the flavanone nor the benzofuranone product (entry
3), while (4S,5R)-Ru319 provided flavanone 3 in a respectable
76% yield but with almost no enantioenrichment (7% ee)
(entry 4). We next tested two new chiral ruthenium catalysts
both containing one cyclometalating ligand and a stereogenic
metal center (with exclusively achiral ligands). The catalyst Λ-
Ru4, which bears a cyclometalating phenylbenzothiazole ligand
and a coordinated 1,10-phenanthroline, provided the flavanone
(R)-3 in 99% yield and with 87% ee (entry 5), while Λ-Ru5
bearing a cyclometalating phenylpyrazole ligand instead20
afforded the flavanone (R)-3 with the same almost quantitative
yield but an improved 94% ee (entry 6). These cyclometalated
ruthenium complexes appeared to be highly suitable for the
ring-closing C(sp3)−H insertion reaction to yield flavanones.
Indeed, the cyclometalated ruthenium catalyst Ru(II)−pheox
(R)-Ru6, developed by Iwasa for enantioselective cyclo-
propanations using diazocarbonyl compounds,10e,f,21 is also
capable of catalyzing the conversion 1 → 3, albeit with a
reduced 65% ee (entry 7). Thus, we selected Λ-Ru5 for further
reaction optimization. Reducing the catalyst loading from 2 to
1 mol % provided somewhat inferior results (entry 8), while a
reduction of the reaction temperature from room temperature
to 0 °C slowed the reaction and decreased the enantiose-
lectivity (entry 9). Finally, the mirror-imaged catalyst Δ-Ru5
provided flavanone (S)-3 as expected (entry 10). To
summarize, our best results were achieved using Ru5 at a
catalyst loading of 2 mol % in dichloromethane (0.5 M) at
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Table 1. Initial Experiments and Optimizationa

entry catalyst conditions conv. (%) 2 (%)b 3 (%)b ee (%)c

1 [Rh2(OAc)4] standard 100 69 0
2 Λ-Ru1 standard 63d 7 32 38 (S)
3 Λ-Ru2 standard 100d <5 0
4 (4S,5R)-Ru3 standard 100 0 76 7 (S)
5 Λ-Ru4 standard 100 0 99 87 (R)
6 Λ-Ru5 standard 100 0 99 94 (R)
7 (R)-Ru6 standard 100 0 99 65 (S)
8 Λ-Ru5 1 mol % cat. 92 0 92 92 (R)
9 Λ-Ru5 0 °C 30 0 15 91 (R)
10 Δ-Ru5 standard 100 0 99 94 (S)
a
Standard conditions: 1 (0.25 mmol) in CH2Cl2 (0.5 mL) with catalyst (2.0 mol %) stirred at room temperature for 30 min under an atmosphere
of N2, unless stated otherwise. bDetermined by 1H NMR of the crude products using hexamethylbenzene as internal standard. cEnantioselectivities
determined by HPLC on the chiral stationary phase. dReaction time extended to 16 h.

room temperature (see Supporting Information for the
influence of solvent and catalyst counterion).
Synthesis and Structural Characterization of Λ- and
Δ-Ru5. The synthesis of the new cyclometalated chiral-at-
ruthenium catalyst Ru5 is shown in Scheme 1. Phenylpyrazole
L1 was reacted with [Ru(η6-C6H6)2Cl2]2 in MeCN at 85 °C in
the presence of the base NaOAc, followed by reaction with
1,10-phenanthroline (phen) to provide the racemic complex
rac-Ru7 (see Supporting Information for a determination of
the relative configuration by NMR), which is a diastereomer of
rac-Ru5 (pyridyl cis to the Ru−C bond in Ru5 versus pyridyl
trans to the Ru−C bond in Ru7). Reaction of rac-Ru7 with
(R)-N-benzoyl-tert-butanesulfinamide, (R)-Aux,22 in the pres-
ence of K2CO3 in EtOH at 100 °C in a sealed Schlenk tube
(see Supporting Information for the experimental setup)
afforded the N-sulfinylcarboximidate complex Λ-(S)-Ru8 as a
single stereoisomer in 46% yield. Apparently, the R-stereo-
center of the auxiliary ligand (corresponding to S-configuration
after coordination) can only be matched properly with a Λ-
configuration at the metal center. The complex Δ-(S)-Ru8,
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small amounts of which could be detected by crude 1H NMR,
could not be isolated due to instability on the silica gel column.
To obtain the Δ-configured ruthenium complexes, rac-Ru7
was reacted with (S)-Aux to provide Δ-(R)-Ru8, which is the
mirror image of Λ-(S)-Ru8. Note that an isomerization of the
ligand sphere occurred in the course of the coordination of the
chiral auxiliary ligand.23 Finally, the sulfinylcarboximidate
ligands were replaced with acetonitriles upon reaction with
the weak acid NH4BF4 in MeCN at room temperature to
provide Λ-Ru5 and Δ-Ru5, which were isolated by silica gel
chromatography. The enantiomeric purity of Λ-Ru5 (99:1 er)
was determined by 1H NMR after coordination of a chiral
oxazoline ligand (see Supporting Information for more
details). The chiral-at-ruthenium catalysts Λ-Ru5 and Δ-Ru5
are stable as solids and can be stored in a freezer at −20 °C
under air atmosphere. The enantiomerically pure catalysts are
also stable in the coordinating solvent MeCN, which probably
suppresses the formation of an unstable pentacoordinated
intermediate upon dissociation of one MeCN ligand. However,
slow racemization and decomposition can be observed in other
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Scheme 1. Synthesis of Non-Racemic Catalysts Λ- and Δ-

Ru5

Figure 2. Crystal structure of Λ-Ru5 as an ORTEP drawing with 50%

probability thermal ellipsoids. The tetrafluoroborate counterion is
omitted for clarity (CCDC 2083005).

solvents such as CH2Cl2 (half-life of 47.5 h) or THF (half-life

6.6 h) (see Supporting Information). Due to the high catalytic
activity and the resulting short reaction times, this apparently
does not affect the outcome of reactions performed in the
preferred reaction solvent CH2Cl2.
A crystal structure of Λ-Ru5 is shown in Figure 2 which
confirmed the assignment of the absolute metal-centered
configuration with a left-handed helical topology. The phenyl
ligand of the cyclometalated phenylpyrazole ligand exerts a
strong trans-effect, which is apparent from the increased Ru−N
coordinative bond length of the trans-coordinated acetonitrile
ligand (Ru−N5 = 2.143 Å vs Ru−N6 = 2.032 Å).24 Another
interesting aspect is the 2,4,6-trimethylphenyl (mesityl) N-
substituent of the pyrazole ligand, which is in close vicinity of
the catalyst’s active site by stacking on top of the two
monodentate acetonitrile ligands.
Deuteration Experiments. Deuteration experiments were
performed to assist in understanding the mechanism. A
substrate with a deuterium atom at the diazo carbon (1-d1) Figure 3. Deuteration experiments to confirm a reaction mechanism
provided under standard conditions the deuterated flavanone through concerted C−H insertion of a ruthenium carbene complex.
trans-3-d125 (95% yield, 94% ee) as a single diastereomer KIE determined from relative rates of the non-deuterated and
deuterated substrate (kH/kD) with a catalyst loading of 0.02 mol %
(Figure 3). Likewise, a substrate with a bis-deuterated benzylic
and a reaction time of just 10 min.
methylene group (1-d2) afforded the bis-deuterated flavanone
cis-3-d2 (94% yield, 94% ee) as a single diastereomer. Relative
rates determined with substrates 1 and 1-d2 provided a KIE Computational Analysis. To understand why the cyclo-
(kH/kD) of 2.9. These experiments support a concerted C−H ruthenated catalysts are so effective at promoting enantiose-
insertion of an intermediate ruthenium carbene species in lective ring-closing C−H insertion and suppressing the
which the C−H insertion is the rate limiting step within the competing C−O formation pathway, we performed density
catalytic cycle. functional theory (DFT) calculations. The calculated C−H
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Figure 4. Calculated C−H insertion TSs for flavanone formation catalyzed by Ru5 at the M06L/def2-TZVPP−SDD(Ru), SMD(CH2Cl2)//
B3LYP-D3/def2-SVP, LANL2DZ(Ru) level of theory. Energies are in kcal/mol. Interatomic distances are in Å.

Figure 5. Calculated free energy diagram for the synthesis of flavanone (C−H insertion) or benzofuranone (C−O formation) catalyzed by Ru4 at
the M06L/def2-TZVPP−SDD(Ru), SMD(CH2Cl2)//B3LYP-D3/def2-SVP, LANL2DZ(Ru) level of theory.

insertion transition states (TSs) for Λ-Ru5 leading to the
major and minor flavanone product enantiomers are shown in
Figure 4. Our results showed that for Ru5, the C−H insertion
TS leading to the major flavanone enantiomer (TS-1-major)
preferred the coordination site trans to the Ru−C bond for the
carbene moiety. TS-1-minor, the TS leading to the minor
enantiomer, appeared to prefer the coordination site trans to
the Ru−N bond (see Supporting Information for a more
detailed discussion) and was calculated to be 3.0 kcal/mol
10308
higher in free energy than TS-1-major. This energy difference
is in good agreement with the high enantioselectivity observed
experimentally. Compared to TS-1-minor, TS-1-major
features significantly stronger π−π stacking interactions,
which are highlighted in green between the substrate and the
tricyclic aromatic ligand. We proceeded to perform distortion−
interaction analysis26 to further reveal the origins of the
enantioselectivity. The metal−ligand framework exclusive of
the substrate (highlighted in green) was calculated to be 1.6
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Figure 6. Substrate scope with Λ-Ru5 under standard reaction conditions (Table 1, entry 6). aCatalyst loading of 3 mol % instead. bSee Supporting
Information for the reaction conditions to remove the Boc protecting group. cThe start material was fully consumed but no flavanone was product
detected. dNo reaction occurred under standard reaction conditions.

kcal/mol more distorted in TS-1-minor than in TS-1-major,
indicating that TS-1-major also benefits from a better steric fit
between the substrate and the ligand framework. The top views
of the two TSs (Figure 4) show that TS-1-minor exhibits
substantial deformation of the ligand framework, including a
readily discernible decrease in the dihedral angle between the
two polyaromatic ring systems (see Supporting Information for
a more detailed discussion).
The relative energetics of the C−H insertion and C−O
formation pathways were evaluated for the related catalyst Ru4
(Figure 5). Benzofuranone 2 was calculated to be 1.4 kcal/mol
more stable than the desired flavanone product 3, indicating
that the chemoselectivity for flavanone formation is most likely
due to kinetic control. The most favorable C−H insertion TS
(TS-2, with the carbene coordinating trans to the Ru−N
bond) for Ru4 was calculated to be close in energy to the most
favorable C−O formation TS (TS-3, with the carbene
coordinating trans to the Ru−C bond). Despite having similar
barriers, the energetic fates of the C−H insertion and C−O
formation pathways diverge significantly past the TSs. Due to
the formation of strong C−C and C−H bonds in one
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concerted step, the C−H insertion pathway is essentially non-
reversible with a reversion free energy barrier close to 40 kcal/
mol, further suggesting that the reaction is under kinetic
control.27 The C−O formation pathway, on the other hand,
forms an unstable zwitterionic structure (C4) that is almost
isoenergetic to the C−O formation TS. This zwitterionic
structure is presumably destabilized by the presence of σ-
donating ligands around the Ru center, and dissociation of the
zwitterionic substrate from the Ru center was calculated to be
an additional 5.2 kcal/mol uphill from C4.28 It is also worth
noting that for some conformations and/or coordination
modes, the C−O formation TS could not even be located;
instead, the C−O formation pathway is barrierless and all the
way uphill due to the lack of stabilization for the zwitterionic
intermediate. Catalysts with more sterically demanding ligands
(such as Ru5) also further disfavor the C−O formation
pathway and render it barrierless and thermodynamically
uphill. In short, our calculations supported the idea that σ-
donating cyclometalated ligands are essential for the selective
reactivity for C−H insertion displayed by catalysts such as Ru4
and Ru5.
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Substrate Scope. We next investigated the substrate scope
(Figure 6). The diazoketone substrates are easily accessible
from their respective acetophenones in two steps (70−92%
yield), including a single silica gel purification (see Supporting
Information). First, we incorporated functionalities into the
phenyl moiety of the benzyl ether of 1. Substrates with methyl
substituents in the para-, meta-, or ortho-position afforded the
corresponding flavanones 4−6 in 88−95% yield and with 91−
93% ee. Fluorine, chlorine, or bromine in the para-position
were also well tolerated and provided the corresponding
flavanones 7−9 in 93−95% yield and with 90−91% ee.
Flavanone 10 bearing a bromine in ortho-position was
synthesized in 85% yield and with 86% ee. Flavanones with a
methylester (11), nitrile (12), trifluoromethyl (13), nitro (14),
or tosylate (15) group in the para-position of the phenyl group
were afforded in 91−98% yield and with 87−92% ee. However,
a para-methoxy group reduced the yield of flavanone 16 to
34% although the enantioselectivity remained high (94% ee).
The reason for the low yield is the competing formation of a 5-
membered benzofuranone 16′ which was formed in 64% yield.
The same side reaction is observed with a 1-naphthyl group
(flavanone 17 together with benzofuranone 17′), while a 2-
naphthyl group (flavanone 18) cleanly provided the desired
C−H carbene insertion product (95% yield, 91% ee).
However, replacing the phenyl group with a 2-thiophene did
not result in the formation of any C−H carbene insertion.
Instead, the benzofuranone 19′ was isolated in 43% yield.
Finally, we also introduced substituents into the chromanone
core of the chiral flavanones. Both electron-withdrawing and
electron-donating groups were tolerated, including methyl,
halogens, nitro, methoxy, and a Boc-protected alcohol (20−27,
85−99% yield, 89−96% ee). Flavanone 28 containing a Boc-
protected alcohol both in the chromanone core and the phenyl
substituent was synthesized in 94% yield and with 91% ee.
Likewise, the bis-tosylate 29 was obtained in 97% yield and
with 91% ee. The chiral naphthoflavanone 30 was synthesized
in 99% yield and with 93% ee. Overall, the conversion of
diazoketones to chiral flavanones catalyzed by the chiral-at-
ruthenium catalyst Λ-Ru5 provided a broad variety of chiral
flavanones in up to 99% yield and with up to 96% ee, further
demonstrating the utility of this new approach. For example,
the bis-Boc-protected flavanone 28 could be converted to the
natural flavanone 31 liquiritigenin, an established estrogen
receptor agonist.29 However, we like to point out that this
method is limited to substrates containing benzyl ethers (see
failed formation of 32) and diazoketones without an alkyl
substituent in α-position (see failed conversion of 33 to 34).
■ CONCLUSIONS
In conclusion, we report a new synthetic strategy for accessing
chiral flavanones via enantioselective ring-closing C(sp3)−H
carbene insertion. This approach has been previously elusive
due to the competing formation of an oxonium ylide
intermediate followed by a [1,2]-shift, which leads to a
benzofuranone instead of the desired chromanone scaffold.
The preference for C−H carbene insertion was accomplished
with a cyclometalated chiral ruthenium catalyst. DFT
calculations suggest that the cyclometalating ligand with the
strong electron-donating phenyl-Ru σ-bond disfavors benzo-
furane formation by destabilizing the resulting zwitterionic
intermediate. It is worth noting that the catalyst utilizes
exclusively achiral ligands and derives its chirality solely from a
stereogenic ruthenium center, adding to the growing class of
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Research Article
powerful chiral-at-metal catalysts used in asymmetric catalysis.
Flavanones are considered to be privileged scaffolds30 with a
wide variety of biological functions. The here introduced
method is based on a desirable C(sp3)−H functionalization
and thereby expands the toolbox for the expedite synthesis of
flavanones with new or improved biological functions.
■
*
ASSOCIATED CONTENT
sı Supporting Information
The Supporting Information is available free of charge at
https://pubs.acs.org/doi/10.1021/acscatal.2c02423.
Experimental procedures, analytical data, NMR spectra,
HPLC traces, and crystallographic data (PDF)
Crystallographic data for Ru-pre1 (CCDC 2083007)
(CIF)
Crystallographic data for Λ-(S)-Ru4(Thiazole)Aux
(CCDC 2083006) (CIF)
Crystallographic data for Λ-Ru5 (CCDC 2083005)
(CIF)
■ AUTHOR INFORMATION
Corresponding Authors
Shuming Chen − Department of Chemistry and Biochemistry,
Oberlin College, Oberlin, Ohio 44074, United States;
Email: shuming.chen@oberlin.edu
Eric Meggers − Fachbereich Chemie, Philipps-Universität
Marburg, Marburg 35043, Germany; orcid.org/0000-
0002-8851-7623; Email: meggers@chemie.uni-
marburg.de
Authors
Feng Han − Fachbereich Chemie, Philipps-Universität
Marburg, Marburg 35043, Germany
Peter H. Choi − Department of Chemistry and Biochemistry,
Oberlin College, Oberlin, Ohio 44074, United States
Chen-Xi Ye − Fachbereich Chemie, Philipps-Universität
Marburg, Marburg 35043, Germany; orcid.org/0000-
0003-4534-845X
Yvonne Grell − Fachbereich Chemie, Philipps-Universität
Marburg, Marburg 35043, Germany
Xiulan Xie − Fachbereich Chemie, Philipps-Universität
Marburg, Marburg 35043, Germany
Sergei I. Ivlev − Fachbereich Chemie, Philipps-Universität
Marburg, Marburg 35043, Germany; orcid.org/0000-
0003-4871-825X
Complete contact information is available at:
https://pubs.acs.org/10.1021/acscatal.2c02423
Notes
The authors declare no competing financial interest.
■ ACKNOWLEDGMENTS
E.M. thanks the Deutsche Forschungsgemeinschaft (ME1805/
15-1) and the University of Marburg for funding of this
project. S.C. is grateful to Oberlin College for financial support.
DFT calculations were performed using the SCIURus, the
Oberlin College HPC cluster (NSF MRI 1427949), and the
research allocations awarded by Extreme Science and
Engineering Discovery Environment (XSEDE TG-
CHE210088).
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charge separation and lower the energy of the system, our potential
energy surface scan indicated that the 1,2-shift would have a Co/Zn Bimetallic Catalysis Enables Enantioselective
prohibitively high barrier (∼50 kcal/mol) with the substrate still Alkynylation of Isatins and α-Ketoesters Using Terminal
coordinated to the Ru center. The unfavorability of the 1,2-shift could Alkynes
be due to decreased partial negative charge on the destination carbon
site arising from Ru coordination (Mulliken charge −0.03 on the Rui-Zhi Huang, Yu Zhao, et al.
carbon compared to −0.43 without Ru coordination), as well as steric OCTOBER 31, 2022
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Asymmetric Synthesis of Chiral Cyclopropanes from
Sulfoxonium Ylides Catalyzed by a Chiral-at-Metal Rh(III)
Complex
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