Synlett 2010(13): 2041-2044  
DOI: 10.1055/s-0030-1258540
CLUSTER
© Georg Thieme Verlag Stuttgart ˙ New York

Asymmetric CuH-Catalyzed 1,4-Reductions in Water at Room Temperature

Shenlin Huang, Karl R. Voigtritter, John B. Unger, Bruce H. Lipshutz*
Department of Chemistry and Biochemistry, University of California, Santa Barbara, California 93106, USA
Fax: +1(805)8938265; e-Mail: lipshutz@chem.ucsb.edu;
Further Information

Publication History

Received 18 June 2010
Publication Date:
02 August 2010 (eFirst)

Abstract

Taking advantage of micellar catalysis in water, asymmetric hydrosilylation reactions can now be conducted at ambient temperatures using water, and only water, as the global medium.

    References and Notes

  • 1a Review: Deutsch C. Krause N. Lipshutz BH. Chem. Rev.  2008,  108:  2916 
  • 1b Rendler S. Oestreich M. Angew. Chem. Int. Ed.  2007,  46:  498 
  • For selected cases, see:
  • 1c Yun J. Kim D. Lee D. Angew. Chem. Int. Ed.  2006,  45:  2785 
  • 1d Lipshutz BH. Servesko JM. Taft BR. J. Am. Chem. Soc.  2004,  126:  8352 
  • 1e Buchwald SL. Aye Y. Rainka MP. Proc. Natl. Acad. Sci. U.S.A.  2004,  101:  5821 
  • 1f Czekelius C. Carreira EM. Angew. Chem. Int. Ed.  2003,  42:  4793 
  • 2 Lawrence NJ. Drew MD. Bushell SM. J. Chem. Soc., Perkin Trans. 1  1999,  3381 
  • 3 Hays DS. Scholl M. Fu GC. J. Org. Chem.  1996,  61:  6751 
  • 4 Nishiyama H. Shiomi T. Tsuchiya Y. Matsuda I. J. Am. Chem. Soc.  2005,  127:  6972 
  • 5 Sheldon RA. Arends I. Hanefeld U. Green Chemistry and Catalysis   Wiley-VCH; Weinheim: 2007. 
  • 6a Dwars T. Paetzold E. Oehme G. Angew. Chem. Int. Ed.  2005,  44:  7174 
  • 6b Khan MN. Micellar Catalysis   CRC Press; Boca Raton: 2006. 
  • 7 Saito T. Yokozawa T. Ishizaki T. Moroi T. Sayo N. Miura T. Kumobayashi H. Adv. Synth. Catal.  2001,  343:  264 
  • 8a Lipshutz BH. Synlett  2009,  509 
  • 8b Lipshutz BH. Servesko JM. Petersen TB. Papa PP. Lover AA. Org. Lett.  2004,  6:  1273 
  • 9 Lipshutz BH. Ghorai S. Aldrichimica Acta  2008,  41:  59 
  • 10 Narayan S. Muldoon J. Finn MG. Fokin VV. Kolib HC. Sharpless KB. Angew. Chem. Int. Ed.  2005,  44:  3275 
  • 11 Palaprat G. Ganachaud F. Mauzac M. Hemery P. Polymer  2005,  46:  11213 
  • 13a Schmid R. Cereghetti M. Heiser B. Schonholzer P. Hansen H.-J. Helv. Chim. Acta  1988,  71:  897 
  • 13b Schmid R. Foricher J. Cereghetti M. Schonholzer P. Helv. Chim. Acta  1991,  74:  370 
  • 13c Schmid R. Broger EA. Cereghetti M. Crameri Y. Foricher J. Lalonde M. Muller RK. Scalone M. Schoettel G. Zutter U. Pure Appl. Chem.  1996,  68:  131 
  • 14a Togni A. Breutel C. Schnyder A. Spindler F. Landert H. Tijani A. J. Am. Chem. Soc.  1994,  116:  4062 
  • 14b Blaser H.-U. Brieden W. Pugin B. Spindler F. Studer M. Togni A. Top. Catal.  2002,  19: 
  • 15 Lipshutz BH. Servesko JM. Angew. Chem. Int. Ed.  2003,  42:  4789 
  • 16 Lee D. Yang Y. Yun J. Org. Lett.  2007,  9:  2749 
  • 17 Hughes G. Kimura M. Buchwald SL. J. Am. Chem. Soc.  2003,  125:  11253 
  • 18a Bauer I. Maranda L. Young KA. Shimizu Y. Huang S. Tetrahedron Lett.  1995,  36:  991 
  • 18b Walsh LM. Goodman JM. Chem. Commun.  2003,  2616 
  • 19 Lipshutz BH. Lee C.-T. Servesko JM. Org. Lett.  2007,  9:  4713 
  • General Procedure for a CuH-Catalyzed Asymmetric 1,4-Reduction in Water To a 5 mL glass vial was added Cu(OAc)2˙H2O (3 mg, 0.015 mmol) and (R)-3,5-Xyl-MeO-BIPHEP (10.4 mg, 0.015 mmol). After an atmosphere exchange with argon, 2 wt% TPGS-750-M/H2O (2 mL) was added, and the mixture was vigorously stirred for 2 h. Isophorone (75 µL, 0.5 mmol) was added and the reaction continued with stirring for 10 min. PMHS (0.3 mL) was added dropwise to the reaction over 6 h. The reaction was stirred vigorously overnight (12 h), then quenched with sat. aq NH4F (0.3 mL) and stirred for an additional 2 h. The resulting solution was filtered through a short plug of silica gel and concentrated under vacuum. The product was purified via silica gel flash chromatography (10% Et2O-hexanes) to afford the desired 3,3,5-trimethyl-cyclohexanone as a colorless oil (62 mg, 88%). The ee was determined by chiral GC on a β-DEX SM column, 100 ˚C isotherm, 1 mL/min; racemic t R = 13.67 and 14.81 min; nonracemic t R = 13.65 (minor) and 14.85 (major), 94% ee. The product spectral data matched those previously reported:
  • 20a Camps F. Coll J. Guitart J. Tetrahedron  1986,  42:  4603 
  • 20b Baker BA. Boskovic ZV. Lipshutz BH. Org. Lett.  2008,  10:  289 
12

Lipshutz, B. H.; Ghorai, S. University of California, Santa Barbara, CA, in preparation. TPGS-750-M = polyoxyethanyl-α-tocopheryl succinate.