J. Holz, A. Monsees, A. Bçrner et al.
Chem. Int. Ed. 1998, 37, 1931–1933; M. J. Burk, G. Casy, N. B. John-
son, J. Org. Chem. 1998, 63, 6084–6085;
Acknowledgements
[15] M. J. Burk, M. F. Gross, T. G. P. Harper, C. S. Kalberg, J. R. Lee, J. P.
Martinez, Pure Appl. Chem. 1996, 68, 37–44; “The Application of
DuPHOS Rhodium(i) Catalysts for Commercial Scale Asymmetric
Hydrogenation”: C. J. Cobley, N. B. Johnson, I. C. Lennon, R.
McCague, J. A. Ramsden, A. Zanotti-Gerosa, in Asymmetric Cataly-
sis on Industrial Scale (Eds.: H.-U. Blaser, E. Schmidt) Wiley-VCH,
Weinheim, 2004.
The authors are grateful for the financial support provided by Degussa
AG (Hanau) and the Fonds der Chemischen Industrie. It is a pleasure
for us to acknowledge highly skilled technical assistance by G. Wenzel
and H. Borgwaldt. We are thankful for the valuable advice from Prof.
Dr. K. Drauz (Degussa AG) and Prof. Dr. M. Beller (IfOK Rostock).
We thank Dr. C. Fischer and S. Buchholz for the GC and HPLC analy-
ses.
[16] A. Yanagisawa, H. Nakashima, A. Ishiba, H. Yamamoto, J. Am.
Chem. Soc. 1996, 118, 4723–4724; R. W. Barnhart, D. A. McMorran,
B. B. Bosnich, Chem. Commun. 1997, 589–590; A. A. Boezio, J. Pyt-
kowicz, A. CôtØ, A. B. Charette, J. Am. Chem. Soc. 2003, 125,
14260–14261; A. CôtØ, A. A. Boezio, A. B. Charette, Angew.
Chem. 2004, 116, 6687–6690; Angew. Chem. Int. Ed. 2004, 43, 6525–
6528; C. Korff, G. Helmchen, Chem. Commun. 2004, 530–531.
[17] For an excellent review, see T. P. Clark, C. R. Landis, Tetrahedron:
Asymmetry 2004, 15, 2123–2137, and references therein.
[18] For more recent works, see: a) G. Hoge, J. Am. Chem. Soc. 2004,
126, 9920–9921; b) G. MalaisØ, S. Ramdeehul, J. A. Osborn, L.
Barloy, N. Kyrisakas, R. Graff, Eur. J. Inorg. Chem. 2004, 3987–
4001; c) A. Zhang, T. V. RajanBabu, Org. Lett. 2004, 6, 3159–3161;
d) S. Basra, J. G. de Vries, D. J. Hyett, G. Harrison, K. M. Heslop, A.
G Orpen, P. G. Pringle, K. von der Luhe, Dalton Trans. 2004, 1901–
1905; e) G. Hoge, B. Samas, Tetrahedron: Asymmetry 2004, 15,
2155–2157; f) for chiral 3,4-diazoaphospholanes, see: T. P. Clark,
C. R. Landis, S. L. Freed, J. Klosin, K. A. Abboud, J. Am. Chem.
Soc. 2005, 127, 5040–5042, and references therein.
[1] a) J. M. Brown in Comprehensive Asymmetric Catalysis,Vol. I (Eds.:
E. N. Jacobsen, A. Pfaltz, H. Yamamoto) Springer, Berlin, 1999,
pp. 121–182; b) T. Ohkuma, M. Kitamura, R. Noyori In Catalytic
Asymmetric Synthesis (Ed.: I. Ojima), Wiley-VCH, New York, 2000,
pp. 1–110; c) H.-U. Blaser, B. Pugin, F. Spindler, J. Mol. Catal. A
2005, 231, 1–20.
[2] For recent reviews see: a) M. DiØguez, O. Pàmies, A. Ruiz, Y. Diaz,
S. Castillón, C. Claver, Coord. Chem. Rev. 2004, 248, 2165–2192;
b) T. T.-L. Au-Yueng, A. S. C. Chan, Coord. Chem. Rev. 2004, 248,
2151–2164; c) P. Barbara, C. Bianchini, G. Giambastiani, S. L. Pari-
sel, Coord. Chem. Rev. 2004, 248, 2131–2150; d) W. Tang, X. Zhang,
Chem. Rev. 2003, 103, 3029–3069.
[3] Review: K. Inoguchi, S. Sakuraba, K. Achiwa, Synlett 1992, 169–
178.
[4] a) T. V. RajanBabu, T. A. Ayers, G. A. Halliday, K. K. You, J. C.
Calabrese, J. Org. Chem. 1997, 62, 6012–6028; b) T. V. RajanBabu,
T. A. Ayers, A. L. Casalnuovo, J. Am. Chem. Soc. 1994, 116, 4101–
4102; c) T. V. RajanBabu, B. Radetich, K. K. You, T. A. Ayers, A. L.
Casalnuovo, J. C. Calabrese, J. Org. Chem. 1999, 64, 3429–3447.
[5] a) Z. Herseczki, I. Gergely, C. Hegedüs, À. Szçllçsy, J. Bakos, Tetra-
hedron: Asymmetry 2004, 15, 1673–1676; b) N. V. Dubrovina, V. I.
Tararov, A. Monsees, A. Spannenberg, I. D. Kostas, A. Bçrner, Tet-
rahedron: Asymmetry 2005, 16, 3640–3649.
[19] A. Marinetti, D. Carmichael, Chem. Rev. 2002, 102, 201–230.
[20] a) M. Ostermeier, J. Priess, G. Helmchen, Angew. Chem. 2002, 114,
625–628; Angew. Chem. Int. Ed. 2002, 41, 612–614; b) Y. Yan, X.
Zhang, Tetrahedron Lett. 2006, 47, 1567–1569.
[21] M. J. Burk, (E. I. Du Pont de Nemours and Company), EP 0592552,
US 5329015 (02.07.1991).
[22] For some other “backbones” of bisphospholanes, see for example,
a) ferrocene: M. J. Burk, M. F. Gross, Tetrahedron Lett. 1994, 35,
9363–9366; b) xanthene: P. C. J. Kamer, P. W. N. M. van Leeuwen,
J. N. H. Reek, Acc. Chem. Res. 2001, 34, 895–904; c) phenoxathiin:
P. Dierkes, S. Ramdeehul, L. Barloy, A. De Cian, J. Fischer, P. C. J.
Kamer, P. W. N. M. van Leeuwen, J. A. Osborn, Angew. Chem. 1998,
110, 3299–3301; Angew. Chem. Int. Ed. 1998, 37, 3116–3118;
d) Benzo(b)thiophene: U. Berens, (Solvias AG) WO 03/031456 A2
2003; e) Thiophene: T. Benincori, T. Pilati, S. Rizzo, F. Sannicolo,
M. J. Burk, L. de Ferra, E. Ullucci, O. Piccolo, J. Org. Chem. 2005,
70, 5436–5441.
[23] DuPHOS (ligands are commercialized by DowPharma), TangPHOS
(W. Tang, X. Zhang, Angew. Chem. 2002, 114, 1682–1684; Angew.
Chem. Int. Ed. 2002, 41, 1612–1614; ligand is commercialized by
ChiralQuest), Butiphane (Ref. 22d; ligand is commercialized by Sol-
vias AG) and RoPHOS (J. Holz, M. Quirmbach, U. Schmidt, D.
Heller, R. Stürmer, A. Bçrner, J. Org. Chem. 1998, 63, 8031–8034;
ligands are commercialized by Solvias AG). Some other bisphospho-
lanes derived from d-mannitol (W. Li, Z. Zhang, D. Xiao, X. Zhang,
Tetrahedron Lett. 1999, 40, 6701–6704; W. Li, Z. Zhang, D. Xiao, X.
Zhang, J. Org. Chem. 2000, 65, 3489–3496; ligands are commercial-
ized by ChiralQuest).
[6] a) B. D. Vineyard, W. S. Knowles, M. J. Sabacky, G. L. Bachman,
D. J. Weinkauff, J. Am. Chem. Soc. 1977, 99, 5946–5952; b) W. S.
Knowles, Acc. Chem. Res. 1983, 16, 106–112; c) I. D. Gridnev, T.
Imamoto, Acc. Chem. Res. 2004, 37, 633–644, and references there-
in.
[7] a) P. W. N. M. van Leeuwen, P. C. J. Kamer, J. N. H. Reek, P. Dier-
kes, Chem. Rev. 2000, 100, 2741–2769; b) P. Dierkes, P. W. N. M. van
Leeuwen, J. Chem. Soc. Dalton Trans. 1999, 1519–1529.
[8] a) Z. Zhang, H. Qian, J. Longmire, X. Zhang, J. Org. Chem. 2000,
65, 6223–6226; b) C.-J. Wang, X. Sun, X. Zhang, Angew. Chem.
2005, 117, 5013–5015; Angew. Chem. Int. Ed. 2005, 44, 4933–4935.
[9] S. Jeulin, S. Duprat de Paule, V. Ratovelomanana-Vidal, J.-P. GenÞt,
N. Champion, P. Dellis, Angew. Chem. 2004, 116, 324–329; Angew.
Chem. Int. Ed. 2004, 43, 320–325.
[10] H. Shimizu, T. Ishizaki, T. Fujiwara, T. Saito, Tetrahedron: Asymme-
try 2004, 15, 2169–2172.
[11] A. Miyashita, A. Yasuda, H. Takaya, K. Toriumi, T. Ito, T. Souchi,
R. Noyori, J. Am. Chem. Soc. 1980, 102, 7932–7934; X. Wan, Y.
Sun, Y. Luo, D. Li, Z. Zhang, J. Org. Chem. 2005, 70, 1070–1072; H.
Shimizu, I. Nagasaki, T. Saito, Tetrahedron 2005, 61, 5402–5432, and
references therein.
[12] A. Togni, C. Breutel, A. Schnyder, F. Spindler, H. Landert, A.
Tijani, J. Am. Chem. Soc. 1994, 116, 4062–4066; H.-U. Blaser, Adv.
Synth. Catal. 2002, 344, 17–31; F. Spindler, C. Malan, M. Lotz, M.
Kesselgruber, U. Pittelkow, A. Rivas-Nass, O. Briel; H.-U. Blaser,
Tetrahedron: Asymmetry 2004, 15, 2299–2306.
[24] J. Holz, A. Monsees, H. Jiao, J. You, I. V. Komarov, C. Fischer, K.
Drauz, A. Bçrner, J. Org. Chem. 2003, 68, 1701–1707.
[25] J. Almena, A. Monsees, R. Kadyrov, T. H. Riermeier, B. Gotov, J.
Holz, A. Bçrner, Adv. Synth. Catal. 2004, 346, 1263–1266.
[26] For a first industrial application, see: F. Klingler, M. Steigerwald, R.
Ehlenz, (Boehringer Ingelheim Pharma GmbH & Co. KG) DE
10313118A1, 2004.
[27] The whole family of new bisphospholanes are now summarized
under the trade name catASiumM. Ligands and metal complexes
are available from Degussa Homogeneous Catalysts.
[28] The new route also circumvents the claims of a Du Pont de Nem-
ours and Co. patent: M. J. Burk, US 5171892 (15.12.1992), which re-
stricts the industrial application of several bisphospholane ligands.
[13] a) M. J. Burk, J. E. Feaster, R. L. Harlow, Organometallics 1990, 9,
2653–2655; b) M. J. Burk, J. E. Feaster, R. L. Harlow, Tetrahedron:
Asymmetry 1991, 2, 569–592; c) M. J. Burk, J. Am. Chem. Soc. 1991,
113, 8518–8519; d) M. J. Burk, J. E. Feaster, W. A. Nugent, R. L.
Harlow, J. Am. Chem. Soc. 1993, 115, 10125–10138.
[14] M. J. Burk, M. F. Gross, J. P. Martinez, J. Am. Chem. Soc. 1995, 117,
9375–9376; M. J. Burk, T. G. P. Harper, C. S. Kalberg, J. Am. Chem.
Soc. 1995, 117, 4423–4424; M. J. Burk, F. Bienewald, M. Harris, A.
Zanotti-Gerosa, Angew. Chem. 1998, 110, 2034–2037; Angew.
5012
ꢀ 2006 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Chem. Eur. J. 2006, 12, 5001 – 5013