pubs.acs.org/joc
iridium6,7 complexes is an efficient and attractive approach
Synthesis of Chiral Aminophosphines from Chiral
Aminoalcohols via Cyclic Sulfamidates
to desired single enantiomer products. Combinations of
these transition metals and a variety of chiral ligands provide
a wide range of catalysts for asymmetric hydrogenation. The
highly modular nature of chiral aminophosphine ligands
and their derivatives play a very important role in such
reactions.8,9 These single enantiomer chiral compound in-
corporating phosphorus and nitrogen donor atoms is of
increasing interest for applications in enantioselective cata-
lysis. Chelating aminophosphines have a combination of
hard Lewis base (nitrogen) and soft Lewis base (phospho-
rus) centers which make these ligands particularly useful in a
variety of catalytic reactions.10,11 In the 1990s, Noyori and
co-workers first developed the efficient RuCl2(diphosphine)-
(diamine) catalytic system for the hydrogenation of simple
ketones.12 This was also shown to be useful for the hydro-
genation of imines.13 Subsequently, researchers have shown
that RuCl2(diphosphine)(aminophosphine) and RuCl2(ami-
nophosphine)2 complexes are very efficient catalysts for the
hydrogenation of simple ketones and imines as well.14,15
Nevertheless, the available methods for the preparation of
chiral aminophosphines remain limited. This has restricted
the development and application of RuCl2(diphosphine)-
(aminophosphine) or RuCl2(aminophosphine)2 catalyst sys-
tems in asymmetric hydrogenation and other catalytic
applications. The most established protocol for the prepara-
tion of aminophosphines involves nucleophilic phosphide
Rongwei Guo,* Shuiming Lu, Xuanhua Chen,
Chi-Wing Tsang, Wenli Jia, Christine Sui-Seng,
Dino Amoroso, and Kamaluddin Abdur-Rashid*
Kanata Chemical Technologies Inc., 101 College Street,
Office 230, MaRS Center, South Tower, Toronto, ON,
Canada, M5G 1L7
rongwei@kctchem.com; kamal@kctchem.com
Received November 11, 2009
Protic aminophosphines with multiple chiral centers were
synthesized in good yields and high purity by the nucleo-
philic ring-opening of N-protected cyclic sulfamidates
with metal phosphides, followed by hydrolysis and de-
protection. This synthetic approach is clean, scalable, and
high yielding. The method provides an efficient alterna-
tive route for the synthesis of chiral aminophosphines.
(6) (a) Zhu, S. F.; Xie, J. B.; Zhang, Y. Z.; Li, S.; Zhou, Q. L. J. Am. Chem.
Soc. 2006, 128, 12886. (b) Xiao, D.; Zhang, X. Angew. Chem., Int. Ed. 2001,
40, 3425. (c) Lam., K. H.; Xu, L.; Feng, L.; Fan, Q. H.; Lam, F. L.; Lo, W. H.;
Chan, A. S. C. Adv. Synth. Catal 2005, 347, 1755.
(7) (a) Uematsu, N.; Fujii, A.; Hashiguchi, S.; Ikariya, T.; Noyori, R.
J. Am. Chem. Soc. 1996, 118, 4916. (b) Wu, J.; Wang, F.; Ma, Y.; Cui, X.;
Cun, L.; Zhu, J.; Deng, J.; Yu, B. Chem. Commun. 2006, 16, 1766. (c)
Ohkuma, T.; Noyori, R. Compr. Asymmetric Catal., Suppl. 2004, 1, 43–53.
(8) (a) Amoroso, D.; Graham, T.; Guo, R.; Tsang, C. W.; Abdur-Rashid,
K. Aldrichim. Acta 2008, 41, 15. (b) Fang, Y. Q.; Jacobsen, E. N. J. Am.
Chem. Soc. 2008, 130, 5660. (c) Zeng, W.; Chen, G. Y.; Zhou, Y. G.; Li, Y. X.
J. Am. Chem. Soc. 2007, 129, 750. (d) Kawamura, K.; Fukuzawa, H.;
Hayashi, M. Org. Lett. 2008, 10, 3509.
(9) (a) Li, X.; Jia, X.; Xu, L.; Kok, S. H. L.; Yip, C. W.; Chan, A. S. C.
Adv. Synth. Catal. 2005, 347, 1904. (b) Deng, J.; Duan, Z. C.; Huang, J. D.;
Hu, X. P.; Wang, D. Y.; Yu, S. B.; Xu, X. F.; Zheng, Z. Org. Lett. 2007, 9,
4825. (c) Boaz, N. W.; Mackenzie, E. B.; Debenham, S. D.; Large, S. E.;
Ponasik, J. A. Jr. J. Org. Chem. 2005, 70, 1872. (d) Boaz, N. W.; Large, S. E.;
Ponasik, J. A.; Moore, M. K.; Barnette, T.; Nottingham, W. D. Org. Process
Res. Dev. 2005, 9, 472.
The asymmetric hydrogenation of CdC, CdO, and CdN
double bonds catalyzed by rhodium,1-3 ruthenium,4,5 or
(1) (a) Kagan, H. B.; Dang, T. P. J. Chem. Soc. D 1971, 10, 481. (b)
Kagan, H. B.; Dang, T. P. J. Am. Chem. Soc. 1972, 94, 6429. (c) Burk, M. J.;
Feaster, J. E.; Nugent, W. A.; Harlow, R. L. J. Am. Chem. Soc. 1993, 127,
11934. (d) Zhu, G.; Cao, P.; Jiang, Q.; Zhang, X. J. Am. Chem. Soc. 1997,
119, 1799. (e) Jiang, Q.; Xiao, D.; Zhang, Z.; Chao, P.; Zhang, X. Angew.
Chem., Int. Ed. 1999, 38, 516. (f ) Imamoto, T.; Sugita, K.; Yoshida, K. J. Am.
Chem. Soc. 2005, 127, 11934.
(2) (a) Chan, A. S. C.; Hu, W.; Pai, C. C.; Lau, C. P.; Jiang, Y.; Mi, A.;
Yan, M.; Sun, J.; Lou, R.; Deng, J. J. Am. Chem. Soc. 1997, 119, 9570. (b)
Chan, A. S. C.; Zhang, F. Y.; Yip, C. W. J. Am. Chem. Soc. 1997, 119, 4080.
(c) Clyne, D. S.; Mermet-Bouvier, Y. C.; Nomura, N.; RajanBabu, T. V.
J. Org. Chem. 1999, 64, 7601.
(3) (a) Reetz, M. T.; Mehler, G. Angew. Chem., Int. Ed. 2000, 39, 3889. (b)
van den Berg, M.; Minnaars, A. J.; Schudde, E. P.; van Esch, J.; de Vries,
A. H. M.; de Vries, J. G.; Feringa, B. L. J. Am. Chem. Soc. 2000, 122, 11539.
(c) Hu, A. G.; Fu, Y.; Xie, J. H.; Zhou, H.; Wang, L. X.; Zhou, Q. L. Angew.
Chem., Int. Ed. 2002, 41, 2348.
(10) (a) Coutelier, O.; Nowogrocki, G.; Paul, J. F.; Mortreux, A. Adv.
Synth. Catal. 2007, 349, 2259. (b) Bonnaventure, I.; Charette, A. B. J. Org.
Chem. 2008, 73, 6330.
(11) (a) Guo, R.; Morris, R. H.; Song, D. J. Am. Chem. Soc. 2005, 127,
516. (b) Kuriyama, M.; Nagai, K.; Yamada, K.; Miwa, Y.; Taga, T.;
Tomioka, K. J. Am. Chem. Soc. 2002, 124, 8932.
(4) (a) Pai, C. C.; Lin, C. W.; Lin, C. C.; Chen, C. C.; Chan, A. S. C. J. Am.
Chem. Soc. 2001, 123, 3186. (b) Saito, T.; Yokozawa, T.; Ishizaki, T.; Moroi,
T.; Sayo, N.; Miura, T.; Kumobayashi, H. Adv. Synth. Catal. 2001, 343, 264.
(c) Pye, P. J.; Rossen, K.; Reamer, R. A.; Tsou, N. N.; Volante, R. P.; Reider,
P. J. J. Am. Chem. Soc. 1997, 119, 6207. (d) Xie, J. H.; Wang, L. X.; Fu, Y.;
Zhu, S. F.; Fan, B. M.; Duan, H. F.; Zhou, Q. L. J. Am. Chem. Soc. 2003, 125,
4404.
(5) (a) Takaya, H.; Ohta, T.; Mashima, K. Yukagaku 1990, 39, 866. (b)
Hashiguchi, S.; Fujii, A.; Takehara, J.; Ikariya, T.; Noyori, R. J. Am. Chem.
Soc. 1995, 117, 7562. (c) Gao, J. X.; Ikariya, T.; Noyori, R. Organometallics
1996, 15, 1087. (d) Fujii, A.; Hashiguchi, S.; Uematsu, N.; Ikariya, T.;
Noyori, R. J. Am. Chem. Soc. 1996, 118, 2521. (e) Guo, R.; Elpelt, C.; Chen,
X.; Song, D.; Morris, R. H. Chem. Commun. 2005, 24, 3050. (f ) Guo, R.;
Chen, X.; Elpelt, C.; Song, D.; Morris, R. H. Org. Lett. 2005, 7, 1757.
(12) (a) Doucet, H.; Ohkuma, T.; Murata, K.; Yokozawa, T.; Kozawa,
M.; Katayama, E.; England, A. F.; Ikariya, T.; Noyori, R. Angew. Chem.,
Int. Ed. 1998, 37, 1703. (b) Ohkuma, T.; Koizumi, M.; Doucet, H.; Pham, T.;
Kozawa, M.; Murata, K.; Katayama, E.; Yokozawa, T.; Ikariya, T.; Noyori,
R. J. Am. Chem, Soc. 1998, 120, 13529.
(13) (a) Abdur-Rashid, K.; Lough, A. J.; Morris, R. H. Organometallics
2001, 20, 1047–1049. (b) Abdur-Rashid, K.; Lough, A. J.; Morris, R. H.
Organometallics 2000, 19, 2655–2657. (c) Cobley, C. J.; Henschke, J. P.;
Ramsden, J. A. PCT Int. Appl. WO 2002008169 A1, 2003. (d) Cobley, C. J.;
Henschke, J. P. Adv. Synth. Catal. 2003, 345, 195.
(14) Guo, R.; Lough, A. J.; Morris, R. H.; Song, D. Organometallics
2004, 23, 5524.
(15) (a) Abdur-Rashid, K.; Morris, R. H. PCT Int. Appl. WO 2003097571
A1, 2003. (b) Abdur-Rashid, K. PCT Int. Appl. WO 2005056513 A1, 2005.
DOI: 10.1021/jo902302c
r
Published on Web 12/23/2009
J. Org. Chem. 2010, 75, 937–940 937
2009 American Chemical Society