Journal of the American Chemical Society
Article
Astruc, D., Ed.; Wiley-VCH: Weinheim, 2002; Chapter 11, p 368.
Scheme 5. Proposed Stereochemical Pathway for the Rh/
(R)-3a-Catalyzed Enantioselective 1,4-Addition of
Phenylboronic Acid to 2-Cyclohexan-1-one
(c) Gibson, S. E.; Ibrahim, H. Chem. Commun. 2002, 2465. (d) Kundig,
̈
E. P.; Pache, S. H. Sci. Synth. 2003, 2, 155. (e) Salzer, A. Coord. Chem.
Rev. 2003, 242, 59. (f) Schmalz, H.-G.; Dehmel, F. In Transition Metals
for Organic Synthesis. Building Blocks and Fine Chemicals; Beller, M.,
Bolm, C., Eds.; Wiley-VCH: Weinheim, 2004, Vol. 1, Chapter 3.12, p
601. (g) Transition Metal Arene π-Complexes in Organic Synthesis and
Catalysis; Kundig, E. P., Ed.; Springer, Berlin, 2004, Topics in
̈
Organometallic Chemistry Vol. 7. (h) Uemura, M. Org. React. 2006,
67, 217. (i) Rosillo, M.; Dominguez, G.; Perez-Castells, J. Chem. Soc.
Rev. 2007, 36, 1589.
(3) (a) Majdalani, A.; Schmalz, H.-G. Tetrahedron Lett. 1997, 38,
4545. (b) Schellhaas, K.; Schmalz, H.-G.; Bats, J. W. Chem.Eur. J.
1998, 4, 57. (c) Ratini, H.; Kundig, E. P. Org. Lett. 1999, 1, 1997.
̈
(d) Kamikawa, K.; Uemura, M. Synlett 2000, 938. (e) Monovich, L. G.;
Huer
52.
́
ou, Y. L.; Ronn, M.; Molander, G. A. J. Am. Chem. Soc. 2000, 122,
̈
(4) Bolm, C.; Muniz, K. Chem. Soc. Rev. 1999, 28, 51.
̃
(5) (a) Uemura, M.; Miyake, R.; Nishimura, H.; Matsumoto, Y.;
Hayashi, T. Tetrahedron: Asymmetry 1992, 3, 213. (b) The racemate
of compound A was reported in 1988 prior to the Uemura and
Hayashi’s enantiospecific synthesis. See Heppert, J. A.; Thomas-Miller,
The P-olefin chelate coordination of 3 constructs the effective
chiral environment at the rhodium(I) center, and thus, some of
their rhodium complexes display high enantioselectivity in the
asymmetric 1,4- and 1,2-addition reactions of the arylboron
nucleophiles. We have also succeeded in developing the general
and more effective enantiospecific synthetic method of these
phosphine−olefin ligands. The new synthetic method is quite
flexible in terms of the substituent variation, and a library of the
planar-chiral (arene)chromium-based phosphine−olefin ligands
can be established by the combinatorial approach. Among the
newly prepared ligand library, 3g, which is with the bis(3,5-
dimethylphenyl)phosphino group on the η6-arene ring, was
found to be the excellent chiral ligand in the rhodium-catalyzed
asymmetric reactions showing excellent enantioselectivity of up
to 99.9% ee.
M. E.; Milligan, M. L.; Velde, D. V.; Aube,
́
J. Organometallics 1988, 7,
2581.
(6) For selected examples, see: (a) Hayashi, Y.; Sakai, H.; Kaneta, N.;
Uemura, M. J. Organomet. Chem. 1995, 503, 143. (b) Ariffin, A.; Blake,
A. J.; Li, W.-S.; Simpkins, N. S. Synlett 1997, 1453. (c) Han, J. W.;
Jang, H.-Y.; Chung, Y. K. Tetrahedron: Asymmetry 1999, 10, 2853.
(d) Nelson, S. G.; Hilfiker, M. A. Org. Lett. 1999, 1, 1379. (e) Englert,
U.; Haerter, R.; Vasen, D.; Salzer, A. Organometallics 1999, 18, 4390.
(f) Vasen, D.; Salzer, A.; Gerhards, F.; Gals, H.-J.; Sturmer, R.; Bieler,
N. H.; Togni, A. Organometallics 2000, 19, 539. (g) Weber, I.; Jones,
G. B. Tetrahedron Lett. 2001, 42, 6983.
(7) (a) Hayashi, T. In Ferrocenes; Togni, A., Hayashi, T., Eds.; VCH:
Weinheim, 1995; Chapter 2, p 105. (b) Togni, A. In Metallocenes;
Togni, A., Halterman, R. L., Eds.; Wiley-VCH: Weinheim, 1998; Vol.
2, Chapter 11, p 685. (c) Colacot, T. J. Chem. Rev. 2003, 103, 3101.
(d) Barbaro, P.; Bianchini, C.; Giambastiani, G.; Parisel, S. L. Coord.
́
Chem. Rev. 2004, 248, 2131. (e) Arrayas, R. G.; Adrio, J.; Carretero, J.
C. Angew. Chem., Int. Ed. 2006, 45, 7674. (f) Fu, G. C. Acc. Chem. Res.
2006, 39, 853. (g) Ganter, C. In Phosphorus Ligands in Asymmetric
̈
ASSOCIATED CONTENT
* Supporting Information
■
S
Experimental procedures, compound characterization data, and
crystallographic data of [RhCl/(R*)-3]2 ((R*,R*)-4) (CIF
file). This material is available free of charge via the Internet at
Catalysis; Borner, A., Ed.; Wiley-VCH: Weinheim, 2008; Chapter 4.3,
̈
p 393.
(8) (a) Hayashi, T.; Yamamoto, K.; Kumada, M. Tetrahedron Lett.
1974, 4405. (b) Hayashi, T.; Tajika, M.; Tamao, K.; Kumada, M. J.
Am. Chem. Soc. 1976, 98, 3718. (c) Hayashi, T.; Mise, T.; Fukushima,
M.; Kagotani, M.; Nagashima, N.; Hamada, Y.; Matsumoto, A.;
Kawakami, S.; Konishi, M.; Yamamoto, K.; Kumada, M. Bull. Chem.
Soc. Jpn. 1980, 53, 1138. (d) Hayashi, T.; Konishi, M.; Fukushima, M.;
Mise, T.; Kagotani, M.; Tajika, M.; Kumada, M. J. Am. Chem. Soc.
1982, 104, 180.
AUTHOR INFORMATION
■
Corresponding Authors
Notes
The authors declare no competing financial interest.
(9) Ogasawara, M.; Wu, W.-Y.; Arae, S.; Morita, T.; Watanabe, S.;
Takahashi, T.; Kamikawa, K. Angew. Chem., Int. Ed. 2012, 51, 2951.
(10) (a) Takaya, Y.; Ogasawara, M.; Hayashi, T.; Sakai, M.; Miyaura,
N. J. Am. Chem. Soc. 1998, 120, 5579. (b) Hayashi, T.; Takahashi, M.;
Takaya, Y.; Ogasawara, M. J. Am. Chem. Soc. 2002, 124, 5052. For
review, see: (c) Hayashi, T.; Yamasaki, K. Chem. Rev. 2003, 103, 2829.
(d) Hayashi, T. Bull. Chem. Soc. Jpn. 2004, 77, 13. (e) Fagnou, K.;
Lautens, M. Chem. Rev. 2003, 103, 169. (f) Hayashi, T. In Modern
Rhodium-Catalyzed Reactions; Evans, P. A., Ed.; Wiley-VCH:
Weinheim, 2005; p 55.
ACKNOWLEDGMENTS
■
This work was supported by the Cooperative Research
Program from Catalysis Research Center, Hokkaido University
(Grant #11A0003 and #12A0001) and a Grant-in-Aid for
Scientific Research from MEXT, Japan (to M.O. and K.K.).
REFERENCES
■
(1) (a) Halterman, R. L. Chem. Rev. 1992, 92, 965. (b) Wagner, G.;
Herrmann, R. In Ferrocenes; Togni, A.; Hayashi, T., Eds.; VCH:
Weinheim, 1995; Chapter 4, p 173. (c) Togni, A. Angew. Chem., Int.
(11) For selected examples, see: (a) Maire, P.; Deblon, S.; Breher, F.;
Geier, J.; Bohler, C. Ruegger, H.; Schonberg, H.; Grutzmacher, H.
̈
̈
̈
̈
Chem.−Eur. J. 2004, 10, 4198. (b) Shintani, R.; Duan, W.-L.; Nagano,
T.; Okada, A.; Hayashi, T. Angew. Chem., Int. Ed. 2005, 44, 4611.
(c) Shintani, R.; Duan, W.-L.; Okamoto, K.; Hayashi, T. Tetrahedron:
Ed. Engl. 1996, 35, 1475. (d) Richards, C. J.; Locke, A. J. Tetrahedron:
̌
Asymmetry 1998, 9, 2377. (e) Step
̌
nick
̌
a, P.; Lamac,
̌
M. In Ferrocenes;
̌
̌ ̌
Stepnicka, P., Ed.; Wiley: Chichester, 2008; Chapter 7, p 237. (f) Arae,
S.; Ogasawara, M. J. Synth. Org. Chem., Jpn. 2012, 70, 593.
(2) (a) Pape, A. R.; Kaliappan, K. P.; Kundig, E. P. Chem. Rev. 2000,
100, 2917. (b) Rose-Munch, F.; Rose, E. In Modern Arene Chemistry;
Asymmetry 2005, 16, 3400. (d) Piras, E.; Lang, F.; Ruegger, H.; Stein,
̈
̈
D.; Worle, M.; Grutzmacher, H. Chem.−Eur. J. 2006, 12, 5849.
̈
̈
̈
(e) Kasak
́
, P.; Arion, V. B.; Widhalm, M. Tetrahedron: Asymmetry
G
dx.doi.org/10.1021/ja503060e | J. Am. Chem. Soc. XXXX, XXX, XXX−XXX