Synlett 2012; 23(12): 1705-1708
DOI: 10.1055/s-0031-1290697
synpacts
© Georg Thieme Verlag Stuttgart · New York

Controlling Enantioselectivity in Additions to Cyclic Oxocarbenium Ions via Transition-Metal Catalysis

Mary P. Watson*
Department of Chemistry and Biochemistry, University of Delaware, Newark, Delaware 19716, USA, Fax: +1(302)8316335   Email: mpwatson@udel.edu
,
Prantik Maity
Department of Chemistry and Biochemistry, University of Delaware, Newark, Delaware 19716, USA, Fax: +1(302)8316335   Email: mpwatson@udel.edu
› Author Affiliations
Further Information

Publication History

Received: 02 May 2012

Accepted after Revision: 23 May 2012

Publication Date:
29 June 2012 (online)

Dedicated to Professor Robert G. Bergman on the occasion of his 70th birthday

Abstract

Controlling enantioselectivity in additions to oxocarbenium ions remains a challenge in asymmetric catalysis. By using a catalytically generated chiral organometallic intermediate, a copper acetylide, we have developed a novel approach for additions of carbon nucleophiles to cyclic oxocarbenium ions in high enantioselectivities and yields.

 
  • References

    • 2a Braun M, Kotter W. Angew. Chem. Int. Ed. 2004; 43: 514
    • 2b Reisman SE, Doyle AG, Jacobsen EN. J. Am. Chem. Soc. 2008; 130: 7198
    • 2c Moquist PN, Kodama T, Schaus SE. Angew. Chem. Int. Ed. 2010; 49: 7096
    • 2d Umebayashi N, Hamashima Y, Hashizume D, Sodeoka M. Angew. Chem. Int. Ed. 2008; 47: 4196
    • 2e Sodeoka M, Hamashima Y. Chem. Commun. 2009; 5787
    • 2f Maity P, Srinivas H, Watson M. J. Am. Chem. Soc. 2011; 133: 17142
    • 2g Kobayashi S, Arai K, Yamakawa T, Chen Y.-J, Salter MM, Yamashita Y. Adv. Synth. Catal. 2011; 353: 1927
    • 2h Terada M, Tanaka H, Sorimachi K. J. Am. Chem. Soc. 2009; 131: 3430
    • 2i Zhang Q.-W, Fan C.-A, Zhang H.-J, Tu Y.-Q, Zhao Y.-M, Gu P, Chen Z.-M. Angew. Chem. Int. Ed. 2009; 48: 8572
    • 2j Corić I, Müller S, List B. J. Am. Chem. Soc. 2010; 132: 17370
    • 2k Corić I, Vellalath S, List B. J. Am. Chem. Soc. 2010; 132: 8536
    • 2l Corić I, List B. Nature (London) 2012; 483: 315
    • 3a TenBrink RE, Bergh CL, Duncan JN, Harris DW, Huff RM, Lahti RA, Lawson CF, Lutzke BS, Martin IJ, Rees SA, Schlachter SK, Sih JC, Smith MW. J. Med. Chem. 1996; 39: 2435
    • 3b Albrecht U, Lalk M, Langer P. Bioorg. Med. Chem. 2005; 13: 1531
    • 3c Alberts A, Chen J, Kuron G, Hunt V, Huff J, Hoffman C, Rothrock J, Lopez M, Joshua H, Harris E, Patchett A, Monaghan R, Currie S, Stapley E, Albers-Schonberg G, Hensens O, Hirshfield J, Hoogsteen K, Liesch J, Springer J. Proc. Natl. Acad. Sci. U.S.A. 1980; 77: 3957
    • 4a Cozzi PierG, Hilgraf R, Zimmermann N. Eur. J. Org. Chem. 2004; 4095
    • 4b Pu L. Tetrahedron 2003; 59: 9873
    • 4c Yang F, Xi P, Yang L, Lan J, Xie R, You J. J. Org. Chem. 2007; 72: 5457
    • 4d Trost BM, Chan VS, Yamamoto D. J. Am. Chem. Soc. 2010; 132: 5186
    • 4e Takita R, Yakura K, Ohshima T, Shibasaki M. J. Am. Chem. Soc. 2005; 127: 13760
    • 4f Koyuncu H, Dogan Ö. Org. Lett. 2007; 9: 3477
    • 4g Ito J.-I, Asai R, Nishiyama H. Org. Lett. 2010; 12: 3860
    • 4h Frantz DE, Fässler R, Carreira EM. J. Am. Chem. Soc. 2000; 122: 1806
    • 4i Boyall D, Frantz DE, Carreira EM. Org. Lett. 2002; 4: 2605
    • 4j Asano Y, Ito H, Hara K, Sawamura M. Organometallics 2008; 27: 5984
    • 4k Asano Y, Hara K, Ito H, Sawamura M. Org. Lett. 2007; 9: 3901
    • 4l Anand NK, Carreira EM. J. Am. Chem. Soc. 2001; 123: 9687
    • 4m Zhou S, Chen C.-R, Gau H.-M. Org. Lett. 2010; 12: 48
    • 4n Liu L, Wang R, Kang Y.-F, Cai H.-Q, Chen C. Synlett 2006; 1245
    • 4o Chen C, Hong L, Xu Z.-Q, Liu L, Wang R. Org. Lett. 2006; 8: 2277
    • 5a Ahamed M, Todd MH. Eur. J. Org. Chem. 2010; 5935
    • 5b Black DA, Beveridge RE, Arndtsen BA. J. Org. Chem. 2008; 73: 1906
    • 5c Sun Z, Yu S, Ding Z, Ma D. J. Am. Chem. Soc. 2007; 129: 9300
    • 5d Taylor AM, Schreiber SL. Org. Lett. 2006; 8: 143
    • 6a Downey C, Mahoney B, Lipari V. J. Org. Chem. 2009; 74: 2904
    • 6b Downey C, Johnson M, Tracy K. J. Org. Chem. 2008; 73: 3299