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Synthesis 2011(12): 1974-1983  
DOI: 10.1055/s-0030-1260030
PAPER
© Georg Thieme Verlag Stuttgart ˙ New York

Kinetic Resolution of Secondary Alcohols by NHC-Catalyzed Oxidative Esterification

Suman De Sarkar, Anup Biswas, Chie Hoon Song, Armido Studer*
Institute of Organic Chemistry and NRW Graduate School of Chemistry, University of Münster, Corrensstr. 40, 48149 Münster, Germany
Fax: +49(251)8336523; e-Mail: studer@uni-muenster.de;
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Publication History

Received 18 March 2011
Publication Date:
06 May 2011 (online)

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Abstract

Kinetic resolution of racemic secondary alcohols by oxidative esterification using carbene catalysis is described. Good to moderate selectivity has been achieved. N-Heterocyclic carbenes (NHCs) were systematically varied and several aldehydes were included in this study as acyl donors. As an oxidant, a readily available bisquinone-type system was used.

Key words

carbene catalysis - kinetic resolution - oxidative esterification - secondary alcohols - acylazolium ions

    References

  • 1a Berkessel A. Gröger H. Asymmetric Organocatalysis: From Biomimetic Concepts to Applications in Asymmetric Synthesis   Wiley-VCH; Weinheim: 2005. 
    Google Scholar
  • 1b Dalko PI. Enantioselective Organocatalysis: Reactions and Experimental Procedures   Wiley-VCH; Weinheim: 2007. 
    Google Scholar
  • For recent reviews on organocatalysis, see:
  • 2a Valero G. Companyo X. Bravo N. Alba A.-NR. Moyano A. Rios R. Synlett  2010,  1883 
    Google Scholar
  • 2b Zhang ZG. Schreiner PR. Chem. Soc. Rev.  2009,  38:  1187 
    Google Scholar
  • 2c Dondoni A. Massi A. Angew. Chem. Int. Ed.  2008,  47:  4638 
    Google Scholar
  • 2d Pellissier H. Tetrahedron  2007,  63:  9267 
    Google Scholar
  • For recent reviews on NHC-catalyzed transformations, see:
  • 3a Nair V. Vellalath S. Babu BP. Chem. Soc. Rev.  2008,  37:  2691 
    Google Scholar
  • 3b Enders D. Niemeier O. Henseler A. Chem. Rev.  2007,  107:  5606 
    Google Scholar
  • 3c Marion N. Díez-González S. Nolan SP. Angew. Chem. Int. Ed.  2007,  46:  2988 
    Google Scholar
  • 3d Zeitler K. Angew. Chem. Int. Ed.  2005,  44:  7506 
    Google Scholar
  • 4a Lathrop SP. Rovis T. J. Am. Chem. Soc.  2009,  131:  13628 
    Google Scholar
  • 4b Enders D. Henseler A. Adv. Synth. Catal.  2009,  351:  1749 
    Google Scholar
  • 5a DiRocco DA. Oberg KM. Dalton DM. Rovis T. J. Am. Chem. Soc.  2009,  131:  10872 
    Google Scholar
  • 5b Li Y. Shi F.-Q. He Q.-L. You S.-L. Org. Lett.  2009,  11:  3182 
    Google Scholar
  • 6a Burstein C. Glorius F. Angew. Chem. Int. Ed.  2004,  43:  6205 
    Google Scholar
  • 6b Sohn SS. Rosen EL. Bode JW. J. Am. Chem. Soc.  2004,  126:  14370 
    Google Scholar
  • For selected examples of NHC-catalyzed esterifications using internal redox reactions, see:
  • 7a Zeitler K. Rose CA. J. Org. Chem.  2009,  74:  1759 
    Google Scholar
  • 7b Chow KY.-K. Bode JW. J. Am. Chem. Soc.  2004,  126:  8126 
    Google Scholar
  • 7c Reynolds NT. Read de Alaniz J. Rovis T. J. Am. Chem. Soc.  2004,  126:  9518 
    Google Scholar
  • 7d Grasa GA. Güveli T. Singh R. Nolan SP. J. Org. Chem.  2003,  68:  2812 
    Google Scholar
  • For NHC-catalyzed oxidative esterifications using an external oxidant, see:
  • 8a Maki BE. Chan A. Phillips EM. Scheidt KA. Tetrahedron  2009,  65:  3102 
    Google Scholar
  • 8b Noonan C. Baragwanath L. Connon SJ. Tetrahedron Lett.  2008,  49:  4003 
    Google Scholar
  • 8c Miyashita A. Suzuki Y. Nagasaki I. Ishiguro C. Iwamoto K.-I. Higashino T. Chem. Pharm. Bull.  1997,  45:  1254 
    Google Scholar
  • 8d Tam SW. Jimenez L. Diederich F. J. Am. Chem. Soc.  1992,  114:  1503 
    Google Scholar
  • 9a Campbell CD. Duguet N. Gallagher KA. Thomson JE. Lindsay AG. O’Donoghue AC. Smith AD. Chem. Commun.  2008,  3528 
    Google Scholar
  • 9b Thomson JE. Rix K. Smith AD. Org. Lett.  2006,  8:  3785 
    Google Scholar
  • For selected examples of the nonenzymatic kinetic resolution of alcohols, see:
  • 10a Hu B. Meng M. Wang Z. Du W. Fossey JS. Hu X. Deng W.-P. J. Am. Chem. Soc.  2010,  132:  17041 
    Google Scholar
  • 10b Rendler S. Plefka O. Karatas B. Auer G. Fröhlich R. Mück-Lichtenfeld C. Grimme S. Oestreich M. Chem. Eur. J.  2008,  14:  11512 
    Google Scholar
  • 10c Vedejs E. Jure M. Angew. Chem. Int. Ed.  2005,  44:  3974 
    Google Scholar
  • 10d Miller SJ. Acc. Chem. Res.  2004,  37:  601 
    Google Scholar
  • 11a Suzuki Y. Yamauchi K. Muramatsu K. Sato M. Chem Commun.  2004,  2770 
    Google Scholar
  • 11b Kano T. Sasaki K. Maruoka K. Org. Lett.  2005,  7:  1347 
    Google Scholar
  • For recent reports involving acylazolium ions, see:
  • 12a De Sarkar S. Studer A. Angew. Chem. Int. Ed.  2010,  49:  9266 ; Angew. Chem. 2010, 122, 9452
    Google Scholar
  • 12b Zhu ZQ. Xiao JC. Adv. Synth. Catal.  2010,  352:  2455 
    Google Scholar
  • 12c Kaeobamrung J. Mahatthananchai J. Zheng P. Bode JW. J. Am. Chem. Soc.  2010,  132:  8810 
    Google Scholar
  • 12d Ryan SJ. Candish L. Lupton DW. J. Am. Chem. Soc.  2009,  131:  14176 
    Google Scholar
  • For NHC-catalyzed transesterifications, see:
  • 13a Grasa GA. Güveli T. Singh R. Nolan SP. J. Org. Chem.  2003,  68:  2812 
    Google Scholar
  • 13b Nyce GW. Lamboy JA. Connor EF. Waymouth RM. Hedrick JL. Org. Lett.  2002,  4:  3587 
    Google Scholar
  • 14a De Sarkar S. Studer A. Org. Lett.  2010,  12:  1992 
    Google Scholar
  • 14b De Sarkar S. Grimme S. Studer A. J. Am. Chem. Soc.  2010,  132:  1190 
    Google Scholar
  • 14c Guin J. De Sarkar S. Grimme S. Studer A. Angew. Chem. Int. Ed.  2008,  47:  8727 ; Angew. Chem. 2008, 120, 8855
    Google Scholar
  • 16 Bisquinone 14 is readily prepared by treatment of 2,6-di-tert-butylphenol (Aldrich US$37.50/1 kg) with O2; see: Kharasch MS. Joshi BS. J. Org. Chem.  1957,  22:  1439 
    CrossrefGoogle Scholar
  • 17 Enders D. Niemeier O. Balensiefer T. Angew. Chem. Int. Ed.  2006,  45:  1463 
    Google Scholar
  • 19 Brand JP. Siles JIO. Waser J. Synlett  2010,  881 
    Article in Thieme ConnectGoogle Scholar
  • 20 Struble JR. Bode JW. Org. Synth.  2010,  87:  362 
    CrossrefGoogle Scholar
  • 21 Vora HU. Lathrop SP. Reynolds NT. Kerr MS. deAlaniz JR. Rovis T. Org. Synth.  2010,  87:  350 
    CrossrefGoogle Scholar
  • 22 Mahatthananchai J. Zheng P. Bode JW. Angew. Chem. Int. Ed.  2011,  50:  1673 
    CrossrefPubMedGoogle Scholar
  • 23 Kagan HB. Fiaud JC. Top. Stereochem.  1988,  18:  249 
    Google Scholar
  • 24 Tietze LF. Kinzel T. Wolfram T. Chem. Eur. J.  2009,  15:  6199 
    CrossrefGoogle Scholar
  • 25 Luo Y. Herndon JW. Cervantes-Lee F. J. Am. Chem. Soc.  2003,  125:  12720 
    CrossrefGoogle Scholar
  • 26 Ryu E.-H. Cho HK. Zhao Y. Org. Lett.  2007,  9:  5147 
    CrossrefGoogle Scholar
  • 27 Belletire JL. Bills RA. Shackelford SA. Synth. Commun.  2008,  38:  738 
    CrossrefGoogle Scholar
  • 28 Enders D. Han J. Henseler A. Chem. Commun.  2008,  3989 
    Google Scholar
  • 29 Chênevert R. Pelchat N. Morin P. Tetrahedron: Asymmetry  2009,  20:  1191 
    CrossrefGoogle Scholar
15

Scheidt and co-workers reported the desymmetrization of meso-diols using oxidative carbene catalysis; see ref. 8a.

18

The absolute configuration of the major enantiomer of 15a formed using catalyst 8 was determined by comparing the HPLC retention time with that of an authentic sample.