2
870
standpoint, these ligands are not superior to the previously reported AMPP analogues. However, from
a tuning standpoint, they may offer attractive features when considering the modular approach to their
synthesis. As such, the combination of the various derivatizing possibilities with the conversion of the
remaining OH groups of the starting sugar into phosphinite species will lead to attractive structures.
In conclusion, we have demonstrated the applicability of such sugar based electron-donating ligands
in asymmetric catalysis. Even though these ligands are not chiral vicinal diaryl or dialkyl phosphinites,
they are quite effective for the hydrogenation of ketones. Research is under way to investigate both areas
of new synthesis and applications of such ligands.
Acknowledgements
The authors gratefully thank the Centre National de la Recherche Scientifique and the Ministère de la
Recherche et de l’Enseignement Supérieur for financial support and Hoffmann-La Roche for a generous
gift of ketopantolactone.
References
1
2
3
. (a) Noyori, R. In Asymmetric Catalysis in Organic Synthesis; Wiley: New York, 1994. (b) Catalytic Asymmetric Synthesis;
Ojima, I., Ed.; VCH Publishers, Inc.: New York, 1993. (c) Brunner, H.; Zettlmeier, W. Handbook of Enantioselective
Catalysis with Transition Metal Compounds; VCH: Weinheim, 1993; Vol. I and II.
. Lead references to diphosphinite ligands. (a) Hayashi, T.; Tanaka, M.; Ogata, I. Tetrahedron Lett. 1977, 3, 295–296. (b)
Johnson, T. H.; Rangarajan, G. J. Org. Chem. 1980, 45, 62–65. (c) Zhu, G.; Zhang, X. J. Org. Chem. 1998, 63, 3133–3136.
(d) Chan, A. S. C.; Hu, W.; Pai, C.-C.; Lau, C.-P. J. Am. Chem. Soc. 1997, 119, 9570–9571.
. Examples of carbohydrate diphosphinites. (a) Selke, R.; Pracejus, H. J. Mol. Catal. 1986, 37, 213–225 and references
cited therein. (b) Selke, R. ibid. 1986, 37, 227–234. (c) Selke, R.; Schwarze, M.; Baudish, H.; Grassert, I.; Michalik, M.;
Oehme, G.; Stoll, N.; Costisella, B. ibid. 1993, 84, 223–237. (d) Selke, R. J. Organomet. Chem. 1989, 370, 241–248. (e)
Cullen, W. R.; Sugi, Y. Tetrahedron Lett. 1978, 19, 1635–1636. (f) Kreutzfeld, H.-J.; Döbler, C.; Krause, H. W.; Facklam,
B. Tetrahedron: Asymmetry, 1993, 4, 2047–2051. (g) RajanBabu, T. V.; Ayers, T. A.; Casalnuovo, A. L. J. Am. Chem. Soc.
1
994, 62, 6012–6028. (h) RajanBabu, T. V.; Radetich, B.; You, K. K.; Ayers, T. A.; Casalnuovo, A. L.; Calabrese, J. C. J.
Org. Chem. 1999, 64, 3429–3447.
4
. For examples of open chain sugar based diphosphanes. (a) Yamashita, M.; Naoi, M.; Imoto, H.; Oshikawa, T. Bull. Soc.
Chem. Jpn. 1989, 62, 942–944. (b) Chen, Y.; Li, X.; Tong, S.-k.; Choi, M. C. K.; Chan, A. S. C. Tetrahedron Lett. 1999,
4
0, 957–960. (c) Bendaya, A.; Masotti, H.; Peiffer, G.; Siv, C.; Archalvis, A. J. Organomet. Chem. 1993, 444, 41–46. (d)
Choudary, B. M.; Ravichandra Sarma, M.; Dyurga Prasad, A.; Narender, N. Indian J. Chem. 1994, 33B, 152–155.
. (a) Agbossou, F.; Carpentier, J.-F.; Hapiot, F.; Suisse, I.; Mortreux, A. Coord. Chem. Rev. 1998, 180, 1615–1645.
. (a) Agbossou, F.; Carpentier, J.-F.; Hatat, C.; Kokel, N.; Mortreux, A.; Betz, P.; Goddard, R.; Krüger, C. Organometallics
5
6
1
995, 14, 2480–2489. (b) Roucoux, A.; Thieffry, L.; Carpentier, J.-F.; Devocelle, M.; Méliet, C.; Agbossou, F.; Mortreux,
A. Organometallics 1996, 15, 2440–2449. (c) Pasquier, C.; Naili, S.; Pelinski, L.; Brocard, J.; Mortreux, A.; Agbossou, F.
Tetrahedron: Asymmetry 1998, 9, 193–196. (d) Devocelle, M.; Agbossou, F.; Mortreux, A. Synlett 1997, 1306–1308.
. Baggett, N.; Striblehill, P. J. Chem. Soc., Perkin Trans. 1 1977, 1123–1126.
. The chlorodiphenylphosphine and chlorodicyclohexylphosphine were commercially available. The chlorodicyclopentyl-
phosphine was synthesized following the procedure reported in Ref. 6b. 31P NMR always assayed that the reactions went to
7
8
completion over the course of 18 h at room temperature.
1
9
1
. 31P{ H} NMR of the ligands (CD
2
Cl
Giordano, G.; Crabtree, R. Inorg. Synth. 1979, 19, 218–220. Synthesis of
2
: Lahoz, F.; Martin, A.; Esteruelas, M. A.; Sola, E.; Serrano, J. L.; Oro, L. A. Organometallics
2
, δ ppm) 2, 116; 3, 142; 4, 146.
0. Synthesis of [Rh(COD)Cl]
Rh(COD)(OCOCF )]
991, 10, 1794–1799.
2
:
[
3
1
1
1
1. This behavior is following what is generally observed with AMPP ligands as well.
2. Such a trend has been observed twice with AMPP ligands, see: Roucoux, A.; Suisse, I.; Devocelle, M.; Carpentier, J.-F.;
Agbossou, F.; Mortreux, A. Tetrahedron: Asymmetry 1996, 7, 379–382 and Ref. 6a.