1,2-Ferrocenediylazaphosphinines 2: A New Class of Nucleophilic Catalysts for Ring-Opening of Epoxides [1]

Abstract

1,2-Ferrocenediylazaphosphinines (1a-c) have been successfully employed as a new class of nucleophilic catalysts for ring-opening of a range of epoxides, their catalytic efficiency in terms of regioselectivity as well as chemical yield comparing well with the existing catalysts in the literature. In contrast, low enantiomeric excesses have been obtained from the reactions of meso-epoxides catalyzed by (R)-1.

Key words

ferrocenediylazaphosphinines - nucleophilic catalysts - ring-opening - epoxides

References

• 1 For part 1 in the series, see: Hwang G.-H. Ryu E.-S. Park D.-K. Shim SC. Cho CS. Kim T.-J. Jeong JH. Cheong M. Organometallics  2001,  20:  5784 
• For recent reviews on planar chiral ferrocenes, see:
• 2a Richards CJ. Locke AJ. Tetrahedron: Asymmetry  1998,  9:  2377 
• 2b Kagan HB. Riant O. Advances in Asymmetric Synthesis   Vol. 2:  Hassner A. JAI Press Inc.; Greenwich CT: 1997.  p.189 
• For recent reviews and papers on heterocyclic analogues of planar chiral ferrocenes such as phospha- and azaferrocenes, see:
• 3a Ganter C. J. Chem. Soc., Dalton Trans.  2001,  3541 
• 3b Ganter C. Kaulin C. Englert U. Organometallics  1999,  18:  5444 
• 3c Ganter C. Glinsböckel C. Ganter B. Eur. J. Inorg. Chem.  1998,  1163 
• 3d Ganter C. Brassat L. Glinsböckel C. Ganter B. Organometallics  1997,  16:  2862 
• 3e Ogasawara M. Yoshida K. Hayashi T. Organometallics  2001,  20:  1014 
• 3f Ogasawara M. Yoshida K. Hayashi T. Organometallics  2001,  20:  3913 
• 3g Qiao S. Hoic DA. Fu GC. Organometallics  1998,  17:  773 
• 3h Fu GC. Acc. Chem. Res.  2000,  33:  412 ; and references therein
• 4a Lo MM.-C. Fu GC. J. Am. Chem. Soc.  2002,  124:  4572 
• 4b Hodous B. Fu GC. J. Am. Chem. Soc.  2002,  124:  1578 
• 4c Tao B. Ruble JC. Hoic DA. Fu GC. J. Am. Chem. Soc.  1999,  121:  5091 
• 4d Hodous B. Fu GC. J. Am. Chem. Soc.  1999,  121:  2637 
• 4e Ruble JC. Fu GC. J. Am. Chem. Soc.  1998,  120:  11532 
• 4f Liang J. Ruble JC. Fu GC. J. Org. Chem.  1998,  63:  3154 
• 4g Ruble JC. Tweddell J. Fu GC. J. Org. Chem.  1998,  63:  2794 
• 4h Ruble JC. Fu GC. J. Org. Chem.  1996,  61:  7230 
• 4i Tanaka K. Qiao S. Tobisu MM. Lo M.-C. Fu GC. J. Am. Chem. Soc.  2000,  122:  9870 
• 4j Shintani R. Lo MM.-C. Fu GC. Org. Lett.  2000,  2:  3695 
• 4k Rios R. Liang J. Lo MM.-C. Fu GC. Chem. Commun.  2000,  377 
• 4l Lo MM.-C. Fu GC. J. Am. Chem. Soc.  1998,  120:  10270 
• 4m Qiao S. Fu GC. J. Org. Chem.  1998,  63:  4168 
• 5 Garrett CE. Fu GC. J. Org. Chem.  1997,  62:  4534 
• 6 Tao B. Lo MM.-C. Fu GC. J. Am. Chem. Soc.  2001,  123:  353 
• 7 Denmark SE. Barsanti PA. Wong K.-T. Stavenger RA. J. Org. Chem.  1998,  63:  2428 
• 9 For a recent example, see: Kalikhman I. Gostevskii B. Girshberg O. Krivonos S. Kost D. Organometallics  2002,  21:  2551 
• 10a Holmes RR. Chem. Rev.  1996,  96:  927 
• 10b Chuit C. Corriu RJP. Young JC. Chem. Rev.  1993,  93:  1371 
• 10c Haaland A. Angew. Chem., Int. Ed. Engl.  1989,  28:  992 

8

The same reaction, however, did not proceed at all by replacing TMSCl with TMSCN for an unknown reason, as confirmed by quantitative recovery of the starting compound on GC after 24 h.