DOI: 10.1002/chem.
201405528 Communication
& Alkene Carboxylation
Nickel-Catalyzed Direct Carboxylation of Olefins with CO2 :
One-Pot Synthesis of a,b-Unsaturated Carboxylic Acid Salts
Nfflria Huguet,[a] Ivana Jevtovikj,[a] Alvaro Gordillo,[a] Michael L. Lejkowski,[a] Ronald Lindner,[a]
Miriam Bru,[a] Andrey Y. Khalimon,[a] Frank Rominger,[b] Stephan A. Schunk,[c]
Peter Hofmann,[a, b] and Michael Limbach*[a, d]
Dedicated to Prof. Dr. Heinz Hoberg, a pioneer in the field
Abstract: The nickel-catalyzed direct carboxylation of al-
kenes with the cheap and abundantly available C1 build-
ing block carbon dioxide (CO2) in the presence of a base
has been achieved. The one-pot reaction allows for the
direct and selective synthesis of a wide range of a,b-unsa-
turated carboxylates (TON > 100, TOF up to 6 h 1, TON =
turnover number, TOF = turnover frequency). Thus, it is
possible, in one step, to synthesize sodium acrylate from
ethylene, CO2, and a sodium salt. Acrylates are industrially
important products, the synthesis of which has hitherto
required multiple steps.
The exploitation of carbon dioxide (CO2) for the production of
globally used chemicals such as formic acid,[1] is of huge indus-
trial interest, because CO2 is a cheap and abundantly available
C1 building block.[2] Nevertheless, only a few reactions and cat-
alysts enable the straightforward catalytic functionalization of,
for example, alkenes with CO2 to industrially relevant target
molecules such as acrylates. Acrylates and their downstream
products are ubiquitous in daily life as hygiene products, coat-
ings, adhesives, and food preservatives and are globally manu-
factured on a multimillion ton level.
[a] Dr. N. Huguet, Dr. I. Jevtovikj, Dr. A. Gordillo, Dr. M. L. Lejkowski,
Dr. R. Lindner, Dr. M. Bru, Dr. A. Y. Khalimon, Prof. Dr. P. Hofmann,
Dr. M. Limbach
CaRLa (Catalysis Research Laboratory)
Im Neuenheimer Feld 584, 69120 Heidelberg (Germany)
Fax: (+ 49) 621-60-6648957
E-mail: michael.limbach@basf.com
[b] Dr. F. Rominger, Prof. Dr. P. Hofmann
Ruprecht-Karls-Universitt Heidelberg
Organisch-Chemisches Institut
Im Neuenheimer Feld 270, 69120 Heidelberg (Germany)
[c] Dr. S. A. Schunk
hte GmbH
Kurpfalzring 104, 69123 Heidelberg (Germany)
[d] Dr. M. Limbach
BASF SE
Synthesis and Homogeneous Catalysis
Carl-Bosch-Strasse 38, 67056 Ludwigshafen (Germany)
Supporting information for this article is available on the WWW under
http://dx.doi.org/10.1002/chem.201405528.
Chem. Eur. J. 2014, 20, 16858 – 16862
The hydrocarboxylation of activated unsaturated hydrocar-
bons with CO2[3] is an established methodology in organic
chemistry to yield either a,b- (for alkynes),[4] b,g-unsaturated a-
branched (for allenes and 1,3 alkadienes),[5] or a-branched car-
boxylic acid derivatives (for styrenes),[6] but requires the stoi-
chiometric use of reductants (i.e., AlEt3, hydrosilanes, Et2Zn,
RMgX) or directing groups in the substrate.[6c]
The catalytic carboxylation of unsaturated hydrocarbons
with CO2 to a,b-unsaturated carboxylates (i.e., acrylates) has
been difficult for three decades, although, in the 1980s,
Hoberg et al.[7] reported the nickel-catalyzed reaction of al-
kenes and isocyanates (isoelectronic to CO2) to acrylamides.
Since the early results of Hoberg et al., the cleavage of inter-
mediately formed metallalactones, in particular nickelalac-
tones,[8] has been a challenging route for such catalytic reac-
tions: for stereoelectronic reasons, five-membered “Hoberg
complexes” do not readily undergo b-H elimination and their
cleavage with auxiliaries such as electrophiles (i.e., alkyl hal-
ides[9] or protons[9g, 10]), Lewis acids,[9g, 10, 11] a combination of
both,[12] thermally,[9c, 10, 13] or even sonochemically,[10] has not led
to catalysis. The cleavage of nickelalactones with sterically hin-
dered phosphazene bases is slow[11c] and, due to the mutual in-
compatibility of strong bases, Lewis acids, and CO2, catalysis re-
mained a challenge. The same applies for other metals from
groups 4 (Zr),[14] 6 (Mo),[15] 8 (Fe, Ru),[16] 9 (Rh),[17] and 10 (Pd,
Pt).[18]
Only recently have we been able to disclose the first two-
step catalytic synthesis of sodium acrylate from ethylene and
CO2 based on a nickel catalyst (TON 10),[19] as a) we targeted
the exergonic reaction to an acrylic acid salt instead of the
highly endergonic formation of acrylic acid (DG = 21 vs.
59 kJ mol 1[20] in THF) and b) overcame the kinetically unfeasi-
ble b-H elimination from the dtbpe-ligated nickelalactone
1 (DG° = 103 kJ mol 1)[19] by its a-deprotonation with an alkox-
ide base. In this communication we will address the develop-
ment of an efficient one-pot catalyst system, which has previ-
ously been hampered by being limited to a small set of ligands
and substrates, and by the need to separate lactone formation
and its cleavage due to the lack of a base capable of tolerating
CO2.
The reaction of 1 with sodium 2-fluorophenoxide (2 equiv)
led to quantitative decarboxylation to ethylene complex 2 by
31
P NMR, whereas acrylate p-complex 3 was formed in a clean
16858  2014 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
 Communication

though BenzP* was not the most active ligand at 80 8C

(Table 1), it turned out to be robust at elevated temperatures
(TON 10 at 80 8C vs. 35 at 100 8C with sodium 2-fluorophenox-
ide, Table 2). At 120 8C the reductive decarboxylation of nickel-
Scheme 1. Nickelalactone cleavage by sodium 2-fluorophenoxide.
alactone 5 was pronounced and the reaction became slug-
gish.[19, 30]
The electronic and steric influence of substituents on the
phenoxide’s core was crucial for reactivity (Table 2): at 80 8C
reaction in the presence of 10 equiv of base (Scheme 1). Al- sodium phenoxide (50 equiv with respect to Ni(COD)2) as well
though alcoholates (or strong N-bases such as 1,8-diazabicy-
clo[5.4.0]undec-7-ene (DBU)) react irreversibly with CO2 to form
carbonic acid half-esters[21] (or carbaminates),[22] phenoxides are
less nucleophilic. This makes them suitable bases to work with Table 2. Variation of phenoxide, temperature, and stoichiometry.
under CO2-pressure conditions.
Catalytic reactions under CO2 and ethylene pressure (10 and
5 bar) with sodium 3-fluorophenoxide (50 equiv) and the es-
tablished ligand dtbpe[19] gave a TON of 9 (Table 1). Monoden- Entry Phenoxide TON Temp. base/cat.
(DuanPhos) [8C]

1[a] 3 80 50
Table 1. Variation of ligand and solvent.
2[a] 4 80 50

Ligand TON Ligand TON 3[a] 4 80 50

t
d bpe 9 Dcpe 3
dcppe  2 HBF4 2 dippe 6
dippp 5 dippb 2 4[a] 8 (16) 80 50
(S)-BINAPINE 10 (R,R,S,S)-DuanPhos 16
(S,S,R,R)-TangPhos 14 Dcpf 1
(R,R)-QuinoxP* 4 (R,R)-Me-DuPhos 2 5[a] 10 (21) 80 50
2 (DMF) 6[a] 35 (24) 100 50
10 (PhCl, THF) 7[a] 31 (21) 120 50
13 (dioxane) 8[b] 39 (31) 100 100
4
17 (toluene) 9[c] 69 (28) 100 100
10[c] 80 100 200
11[c] 107 100 300
Conditions: Sodium 3-fluorophenoxide (10 mmol), Ni(COD)2 (0.2 mmol),
ligand (0.22 mmol), C2H4 (5 bar), CO2 (10 bar), 20 h. 12[a] 2 80 50

tate phosphines (i.e., PPh3, PtBu3) and small bite-angle ligands
(i.e., dtbpm, dppm) failed in the reaction. Comparably high
TONs (10–16) were obtained with the electron-rich P-stereo-
genic bisphosphine ligands (S)-BINAPINE,[23] (S,S’,R,R’)-Tang-
Phos,[24] (1R,1’R,2S,2’S)-DuanPhos,[25] and (R,R)-BenzP*,[26] where-
as dcpf, HiersoPHOS-1,[27] (R,R)-QuinoxP*[28] and the bisphos-
pholane (R,R)-Me-DuPhos were only moderately active (Table 1,
TON 1–4).[11b] In the homologous series of bidentate ligands
dippe, dippp, and dippb, a C2–3 bridge between the donor
atoms turned out to be beneficial (TON up to 6), whereas
amongst the substituents at the P-donor a tBu or iPr group
gave the highest activity (TONs of 9 and 6, respectively).
The solvent had a major impact on the reaction outcome
(Table 1), whereas ligands such as BenzP* were only moderate-
ly active in DMF (or inactive in MeOH), apolar and aprotic sol-
vents like ethers (THF, dioxane) or even toluene led to higher
reactivity (TON 17). In chlorobenzene oxidative addition to
form NiII turned out to be a limiting side-reaction.[29] Even
13[a] 1 80 50
[a] Ligand (0.22 mmol), Ni(COD)2 (0.2 mmol), CO2 (10 bar), C2H4 (5 bar),
sodium phenoxide (10 mmol); [b] As [a] but ligand (0.11 mmol), Ni(COD)2
(0.1 mmol), 100 8C. [c] As [b] with zinc (10 mmol), CO2 (20 bar), C2H4
(10 bar).
as its derivatives bearing substituents with + I effect in ortho-
position (i.e., sodium 2-methyl- and 2,6-dimethyl-phenoxide,
Table 2, entries 2 and 3) gave comparably low TONs (ca. 4). In
a series of fluoro phenoxides (substituent with I effect), the
meta- or even better ortho-substituted derivative led to an in-
crease in TON but not the para-substituted one (TON 8, 10,
and 2, respectively, cf. Table 2, entries 3, 4, and 12). This trend
holds true for DuanPhos (TON 16 and 21, respectively, cf.
Table 2, entries 4 and 5), albeit at a lower level. The activity of
the phenoxide seems to correlate with its pKa value in H2O

Chem. Eur. J. 2014, 20, 16858 – 16862 www.chemeurj.org 16859  2014 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
 Communication

Terminal, unactivated alkenes or

internal ones did not react to
give the corresponding acrylates,
most likely due to their lower
tendency to form the initial
BenzP*-Ni0-alkene complex simi-
lar to 4 (e.g., cyclopentene, nor-
bonene, (Z)-3-hexene; cf.
Scheme 2), or the corresponding
lactones akin to 5 (e.g., propyl-
ene, 1-hexene).
Apart from ethylene (high
TON of 107; cf. Table 3, entry 1),
the reaction also tolerates differ-
ent functional groups. This is es-
pecially true for 1,3-butadienes:
while n-butylvinylether gave
only traces of sodium 3-me-
thoxy-2-propenoate, the corre-
sponding (E)-1-methoxy-1,3-bu-
tadiene yielded sodium (E,E)-5-
methoxy-2,4-pentadienoate with
Scheme 2. Catalytic cycle and solid-state structure of lactone 5. Ellipsoids drawn at 50 % probability. Hydrogen a reasonably high TON of 99
atoms are omitted for clarity. Selected bond lengths [] and angles [8]: Ni C 1.955(4), Ni O 1.890(2), Ni P1 (Table 3, entries 5 and 6). Similar-
2.1887(10), Ni P2 2.1193(9), O-Ni-C 85.61(13), P-Ni-P 89.04(4).
ly, an (E,Z)-mixture of methyl 2,4-
pentadienoate yielded a mixture
of muconic acid isomers with an
with a maximum for sodium 2-fluorophenoxide (pKa = 8.82).[31] overall TON of 75 (Table 3, entry 7). 2-Vinylpyridine was the
Clearly, a base successful in the reaction is sufficiently Brønst- only substrate that produced the salt of an a-branched a,b-un-
ed-basic to deprotonate nickelalactone 5, and of reasonably saturated acid, albeit with a low TON value (TON 2; Table 3,
poor nucleophilicity to avoid its neutralization by reacting with entry 8). Out of the three different double bonds of the natural
CO2 (Scheme 2). product myrcene, only the least substituted one was trans-
The addition of finely powdered zinc (100 equiv) had a bene- formed with very high (E)-selectivity to the corresponding
ficial effect on the reaction with BenzP* (TON 69 vs. 39; linear a,b-unsaturated carboxylic acid derivative (TON of 11; cf.
Table 2, entry 9). A huge excess of base (300 equiv) increased Table 3, entry 14).
TON further (107 vs. 69 for BenzP*; Table 2, entry 11). Most In conclusion, we have found a robust Nickel catalyst and re-
likely the metal reduced intermediately formed NiII species. The action setup for the one-pot, direct carboxylation of activated
effect was less pronounced for DuanPhos (TON 28 vs. 31; alkenes, such as ethylene, styrenes, and 1,3-dienes with CO2.
Table 2, entries 9 and 10). The a,b-unsaturated carboxylic acid salts are formed in high
Amongst a series of activated alkenes, that is, styrenes, Mi- yields and selectivity for the linear product. This method might
chael acceptors, and 1,3-butadienes, CO2 was only incorporat- pave the way for more efficient routes to basic chemicals such
ed once into the product (Table 3). (E)-Configured starting al- as acrylates, methacrylates, and sorbates, but also enrich the
kenes yielded exclusively (E,E)-configured products. Thus, 1,3- organic chemist’s toolbox to access more complex molecular
butadiene and (E)-piperylene gave exclusively the linear mono- architectures.
carboxylated a,b,g,d-unsaturated carboxylic acids salts
(TON 116 and 90, respectively; Table 3, entries 9 and 10). One
Acknowledgements
or even two alkyl substituents on the double bonds significant-
ly reduced reactivity (cyclohexadiene, isoprene, 2,3-dimethyl-
N.H., I.J., A.G., M.L.L., R.L., M.B., A.Y.K., P.H., and M.L. work at
butadiene, TONs from 7–64; Table 3, entries 11–13). In the case
CaRLa of Heidelberg University, which is co-financed by Heidel-
of isoprene, where there are two terminal double bonds for
berg University, the state of Baden-Wrttemberg, and BASF SE.
a potential reaction with CO2, both products were formed in
Support from Bundesministerium fr Bildung und Forschung
roughly equimolar amounts (TON 7 and 9; Table 3, entry 12).
(BMBF) (grant 01RC1015A) is gratefully acknowledged.
The reaction of styrene and CO2 under optimized reaction con-
ditions yielded only sodium (E)-cinnamate (TON 12; Table 3,
entry 2).[32] Electron-donating or -withdrawing groups in the 4- Keywords: carbon dioxide · catalysis · C C coupling
position of the styrene frame (i.e., R = OMe or CF3) led to a reac- reactions · metallacycles · nickel
tivity drop represented by a TON < 10 (Table 3, entries 3 and 4).

Chem. Eur. J. 2014, 20, 16858 – 16862 www.chemeurj.org 16860  2014 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

Table 3. Substrate scope and limitations.
Entry[a] Alkene[a] Product TON
1 107
2 12 (R = H)
3 2 (R = CF3)
4 8 (R = OMe)
5 traces
6 99
7 75
8 2
9 116
10 90
11 64
12 7:9
gat, D. B rhausen, A. Milcher-
13 7 teros, J. Organomet. Chem. 1991, 411, C11 – C18; c) D. Jin, T. J. Schmeier,
14 11
[a] BenzP* (0.11 mmol), Ni(COD)2 (0.1 mmol), zinc (10 mmol), CO2 (20 bar),
alkene (30 mmol), C2H4 (10 bar), sodium 2-fluoro-phenoxide (30 mmol).
rez, E. Carmona, Organometallics 1993,
[1] R. Tanaka, M. Yamashita, K. Nozaki, J. Am. Chem. Soc. 2009, 131, 14168 –
14169; T. Schaub, R. A. Paciello, Angew. Chem. 2011, 123, 7416 – 7420;
Angew. Chem. Int. Ed. 2011, 50, 7278 – 7282.
[2] For selected recent reviews, see: a) M. Cokoja, C. Bruckmeier, B. Rieger,
W. A. Herrmann, F. E. Khn, Angew. Chem. 2011, 123, 8662 – 8690;
Angew. Chem. Int. Ed. 2011, 50, 8510 – 8537; b) P. Markewitz, W. Kuck-
shinrichs, W. Leitner, J. Linssen, P. Zapp, R. Bongartz, A. Schreiber, T. E.
Mller, Energy Environ. Sci. 2012, 5, 7281 – 7305; c) C. Maeda, Y. Miyaza-
ko, T. Ema, Catal. Sci. Technol. 2014, 4, 1482 – 1497; d) K. Huang, C.-L.
Sun, Z.-J. Shi, Chem. Soc. Rev. 2011, 40, 2435 – 2452; e) B. Yu, Z.-F. Diao,
C.-X. Guo, L.-N. He, J. CO2 Utilization 2013, 1, 60 – 68; f) Y. Tsuji, T. Fuji-
hara, Chem. Commun. 2012, 48, 9956 – 9964; g) M. Mori, Eur. J. Org.
Chem. 2007, 4981 – 4993; h) M. Peters, B. Kçhler, W. Kuckshinrichs, W.
Chem. Eur. J. 2014, 20, 16858 – 16862 www.chemeurj.org
Communication
Leitner, P. Markewitz, T. E. Mller, ChemSusChem 2011, 4, 1216 – 1240;
i) M. Aresta, A. Dibenedetto, A. Angelini, Chem. Rev. 2014, 114, 1709 –
1742.
[3] Highlighted in Y. Zhang, S. N. Riduan, Angew. Chem. 2011, 123, 6334 –
6336; Angew. Chem. Int. Ed. 2011, 50, 6210 – 6212.
[4] a) J. Takaya, N. Iwasawa, J. Am. Chem. Soc. 2008, 130, 15254 – 15255;
b) T. Fujihara, Y. Tani, K. Semba, J. Terao, Y. Tsuji, Angew. Chem. 2012,
124, 11655 – 11658; Angew. Chem. Int. Ed. 2012, 51, 11487 – 11490.
[5] a) T. Fujihara, T. Xu, K. Semba, J. Terao, Y. Tsuji, Angew. Chem. 2011, 123,
543 – 547; Angew. Chem. Int. Ed. 2011, 50, 523 – 527; b) J. Takaya, K.
Sasano, N. Iwasawa, Org. Lett. 2011, 13, 1698 – 1701; Stoichiometric reac-
tion: c) M. Takimoto, M. Mori, J. Am. Chem. Soc. 2001, 123, 2895 – 2896;
d) S. Saito, S. Nakagawa, T. Koizumi, K. Hirayama, Y. Yamamoto, J. Org.
Chem. 1999, 64, 3975 – 3978.
[6] a) C. M. Williams, J. B. Johnson, T. Rovis, J. Am. Chem. Soc. 2008, 130,
14936 – 14937; b) M. D. Greenhalgh, S. P. Thomas, J. Am. Chem. Soc.
2012, 134, 119000 – 111903; c) K. Sasano, J. Takaya, N. Iwasawa, J. Am.
Chem. Soc. 2013, 135, 10954 – 10957; d) L. Gonzlez-Sebastin, M.
Flores-Alamo, J. J. Garca, Organometallics 2012, 31, 8200 – 8207.
[7] a) H. Hoberg, K. Smmermann, A. Milchereit, Angew. Chem. 1985, 97,
320 – 321; Angew. Chem. Int. Ed. Engl. 1985, 24, 325 – 326; b) T. Yamamo-
to, K. Igarashi, S. Komiya, A. Yamamoto, J. Am. Chem. Soc. 1980, 102,
7448 – 7456.
[8] a) K. Shimizu, M. Takimoto, Y. Sato, M. Mori, Org. Lett. 2005, 7, 195 – 197;
b) R. Fischer, D. Walther, G. Br unlich, B. Undeutsch, W. Ludwig, H. Band-
mann, J. Organomet. Chem. 1992, 427, 395 – 407; c) H. Hoberg, Y. Peres,
C. Krger, Y.-H. Tsay, Angew. Chem. 1987, 99, 799 – 800; Angew. Chem.
Int. Ed. Engl. 1987, 26, 771 – 773; d) H. Hoberg, D. Sch fer, J. Organomet.
Chem. 1983, 251, c51 – c53.
[9] a) S. Y. T. Lee, M. Cokoja, M. Drees, Y. Li, J. Mink, W. A. Herrmann, F. E.
Khn, ChemSusChem 2011, 4, 1275 – 1279; b) C. Bruckmeier, M. W. Le-
henmeier, R. Reichardt, S. Vagin, B. Rieger, Organometallics 2010, 29,
2199 – 2202; c) R. Fischer, J. Langer, A. Malassa, D. Walther, H. Gçrls, G.
Vaughan, Chem. Commun. 2006, 2510 – 2512; d) M. Drees, M. Cokoja,
F. E. Khn, ChemCatChem 2012, 4, 1703 – 1712; e) S. Y. T. Lee, A. A.
Ghani, V. D’Elia, M. Cokoja, W. A. Herrmann, J.-M. Basset, F. E. Khn, New
J. Chem. 2013, 37, 3512 – 3517; f) P. N. Plessow, L. Weigel, R. Lindner, A.
Sch fer, F. Rominger, M. Limbach, P. Hofmann, Organometallics 2013,
32, 3327 – 3338; g) H. Hoberg, A. Ballesteros, A. Sigan, C. Jegat, A. Mil-
chereit, Synthesis 1991, 395 – 398.
[10] H. Hoberg, A. Ballesteros, A. Sigan, J. Organomet. Chem. 1991, 403,
C19 – C22.
[11] a) H. Hoberg, A. Ballesteros, A. Sigan, C. J
eit, J. Organomet. Chem. 1991, 407, C23 – C29; b) H. Hoberg, A. Balles-
P. G. Williard, N. Hazari, W. H. Bernskoetter, Organometallics 2013, 32,
2152 – 2159; d) C. Hendriksen, E. A. Pidko, G. Yang, B. Schaeffner, D.
Vogt, Chem. Eur. J. 2014, 20, 12037 – 12040.
[12] G. Br unlich, R. Fischer, B. Nestler, D. Walther, Z. Chem. 2010, 29, 417.
[13] a) K. Sano, T. Yamamoto, A. Yamamoto, Chem. Lett. 1982, 695 – 698; b) K.
Sano, T. Yamamoto, A. Yamamoto, Chem. Lett. 1984, 941 – 944; c) D. Jin,
P. G. Williard, N. Hazari, W. H. Bernskoetter, Chem. Eur. J. 2014, 20, 3205 –
3211.
[14] K. Yamashita, N. Chatani, Synlett 2005, 919 – 922.
[15] a) A. Galindo, A. Pastor, P. J. P
12, 4443 – 4451; b) W. H. Bernskoetter, B. T. Tyler, Organometallics 2011,
30, 520 – 527.
[16] a) H. Hoberg, K. Jenni, C. Krger, E. Raabe, Angew. Chem. 1986, 98, 819 –
820; Angew. Chem. Int. Ed. Engl. 1986, 25, 810 – 811; b) H. Hoberg, K.
Jenni, K. Angermund, C. Krger, Angew. Chem. 1987, 99, 141 – 142;
Angew. Chem. Int. Ed. Engl. 1987, 26, 153 – 155; c) B. Li, S. J. Kyran, A. D.
Yeung, A. A. Bengali, D. J. Darensbourg, Inorg. Chem. 2013, 52, 5438 –
5447.
[17] M. Aresta, E. Quaranta, J. Organomet. Chem. 1993, 463, 215 – 221.
[18] a) T. Yamamoto, K. Sano, K. Osakada, S. Komiya, A. Yamamoto, Y. Kushi,
T. Tada, Organometallics 1990, 9, 2396 – 2403; b) K. Osakada, M.-K. Doh,
F. Ozawa, A. Yamamoto, Organometallics 1990, 9, 2197 – 2198; c) M.
Aresta, C. Pastore, P. Giannoccaro, G. Kovcs, A. Dibenedetto, I. Ppai,
Chem. Eur. J. 2007, 13, 9028 – 9034; d) R. Kakino, K. Nagayama, I. Kayaki,
I. Shimizu, A. Yamamoto, Chem. Lett. 1999, 28, 685 – 686; e) K. Sano, T.
Yamamoto, A. Yamamoto, Bull. Chem. Soc. Jpn. 1984, 57, 2741 – 2747;
16861  2014 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
 Communication

f) K.-T. Aye, D. Coipitts, G. Ferguson, R. J. Puddephatt, Organometallics [25] (1R,1’R,2S,2’S)-DuanPhos = (1R,1’R,2S,2’S)-2,2’-di-tbutyl-2,3,2’,3’-tetrahy-

1988, 7, 1454 – 1456; g) J.-C. Choi, K. Shiraishi, Y. Takenaka, H. Yasuda, T. dro-1H,1’H-(1,1’)biisophosphindolyl, cf. D. Liu, X. Zhang, Eur. J. Org.
Sakakura, Organometallics 2013, 32, 3411 – 3414; h) P. S. Schulz, O. Chem. 2005, 646 – 649.
Walter, E. Dinjus, Appl. Organomet. Chem. 2005, 19, 1176 – 1179. [26] (R,R)-BenzP* = (R,R)-(+)-1,2-bis(tbutylmethylphosphino)benzene, cf. T.
[19] dtbpe = 1,2-bis(di-tert-butylphosphino)ethane, cf. M. L. Lejkowski, R. Imamoto, K. Tamura, Z. Zhang, Y. Horiuchi, M. Sugiya, K. Yoshida, A. Ya-
Lindner, T. Kageyama, G. . Bdizs, P. N. Plessow, I. B. Mller, A. Sch fer,
F. Rominger, P. Hofmann, C. Futter, S. A. Schunk, M. Limbach, Chem. Eur.
J. 2012, 18, 14017 – 14025.
[20] a) P. N. Plessow, A. Sch fer, M. Limbach, P. Hofmann, Organometallics
2014, 33, 3657 – 3668. dtbpe: di-tert-butylphosphinoethane. For studies
on a monodentate DBU-model ligand, cf; b) D. C. Graham, C. Mitchell,
M. I. Bruce, G. F. Metha, J. H. Bowie, M. A. Buntine, Organometallics
2007, 26, 6784 – 6792 (DBU: 1,8-diazabicyclo[5.4.0]undec-7-ene).
[21] W. Behrendt, G. Gattow, M. Dr ger, Z. anorg. allg. Chem. 1973, 397,
237 – 246.
[22] C. Das Neves Gomes, O. Jacquet, C. Villiers, P. Thu
ry, M. Ephritikhine, T. 2257 – 2264.
Cantat, Angew. Chem. 2012, 124, 191 – 194; Angew. Chem. Int. Ed. 2012,
51, 187 – 190.
[23] (S)-BINAPINE = (3S,3’S,4S,4’S,11bS,11’bS)-(+)-4,4’-di-tbutyl-4,4’,5,5’-tetra-
hydro-3,3’-bi-3H-dinaphtho[2,1-c:1’,2’-e]phosphepine, cf. W. Tang, W.
Wang, X. Zhang, Angew. Chem. 2003, 115, 3633 – 3635; Angew. Chem.
Int. Ed. 2003, 42, 3509 – 3511.
[24] (S,S’,R,R’)-TangPhos = (1S,1S’,2R,2R’)-1,1’-di-tbutyl-(2,2’)-diphospholane, cf.
W. Tang, X. Zhang, Angew. Chem. 2002, 114, 1682 – 1684; Angew. Chem.
Int. Ed. 2002, 41, 1612 – 1614.
Chem. Eur. J. 2014, 20, 16858 – 16862 www.chemeurj.org 16862
nagisawa, I. D. Gridnev, J Am Chem. Soc. 2012, 134, 1754 – 1769.
[27] HiersoPHOS-1 = 1’,4-bis(tbutyl)-1,2-bis(diphenylphosphino)-3’-(di-
i
propylphosphino)ferrocene.
[28] (R,R)-QuinoxP* = (R,R)-( )-2,3-bis(tbutylmethylphosphino)quinoxaline, cf.
T. Imamoto, K. Sugita, K. Yoshida, J. Am. Chem. Soc. 2005, 127, 11934 –
11935.
[29] N. Huguet, A. Y. Khalimon, I. Jevtovikj, M. Hanauer, P. N. Plessow, A.
Sch fer, A. Gordillo, M. Bru, F. Rominger, M. Limbach, Organometallics
2014, submitted.
[30] J. Langer, R. Fischer, H. Gçrls, D. Walther, Eur. J. Inorg. Chem. 2007,
[31] M. D. Liptak, K. C. Gross, P. G. Seybold, S. Feldgus, G. C. Shields, J. Am.
Chem. Soc. 2002, 124, 6421 – 6427.
[32] H. Hoberg, Y. Peres, A. Michereit, J. Organomet. Chem. 1986, 307, C38 –
C40.
Received: October 5, 2014
Published online on October 30, 2014
 2014 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim