Kinetic Resolution of Secondary Alcohols by NHC-Catalyzed Oxidative Esterification

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.

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. 

1b Dalko PI. Enantioselective Organocatalysis: Reactions and Experimental Procedures   Wiley-VCH; Weinheim: 2007. 

For recent reviews on organocatalysis, see:

2a Valero G. Companyo X. Bravo N. Alba A.-NR. Moyano A. Rios R. Synlett  2010,  1883 

2b Zhang ZG. Schreiner PR. Chem. Soc. Rev.  2009,  38:  1187 

2c Dondoni A. Massi A. Angew. Chem. Int. Ed.  2008,  47:  4638 

2d Pellissier H. Tetrahedron  2007,  63:  9267 

For recent reviews on NHC-catalyzed transformations, see:

3a Nair V. Vellalath S. Babu BP. Chem. Soc. Rev.  2008,  37:  2691 

3b Enders D. Niemeier O. Henseler A. Chem. Rev.  2007,  107:  5606 

3c Marion N. Díez-González S. Nolan SP. Angew. Chem. Int. Ed.  2007,  46:  2988 

3d Zeitler K. Angew. Chem. Int. Ed.  2005,  44:  7506 

4a Lathrop SP. Rovis T. J. Am. Chem. Soc.  2009,  131:  13628 

4b Enders D. Henseler A. Adv. Synth. Catal.  2009,  351:  1749 

5a DiRocco DA. Oberg KM. Dalton DM. Rovis T. J. Am. Chem. Soc.  2009,  131:  10872 

5b Li Y. Shi F.-Q. He Q.-L. You S.-L. Org. Lett.  2009,  11:  3182 

6a Burstein C. Glorius F. Angew. Chem. Int. Ed.  2004,  43:  6205 

6b Sohn SS. Rosen EL. Bode JW. J. Am. Chem. Soc.  2004,  126:  14370 

For selected examples of NHC-catalyzed esterifications using internal redox reactions, see:

7a Zeitler K. Rose CA. J. Org. Chem.  2009,  74:  1759 

7b Chow KY.-K. Bode JW. J. Am. Chem. Soc.  2004,  126:  8126 

7c Reynolds NT. Read de Alaniz J. Rovis T. J. Am. Chem. Soc.  2004,  126:  9518 

7d Grasa GA. Güveli T. Singh R. Nolan SP. J. Org. Chem.  2003,  68:  2812 

For NHC-catalyzed oxidative esterifications using an external oxidant, see:

8a Maki BE. Chan A. Phillips EM. Scheidt KA. Tetrahedron  2009,  65:  3102 

8b Noonan C. Baragwanath L. Connon SJ. Tetrahedron Lett.  2008,  49:  4003 

8c Miyashita A. Suzuki Y. Nagasaki I. Ishiguro C. Iwamoto K.-I. Higashino T. Chem. Pharm. Bull.  1997,  45:  1254 

8d Tam SW. Jimenez L. Diederich F. J. Am. Chem. Soc.  1992,  114:  1503 

9a Campbell CD. Duguet N. Gallagher KA. Thomson JE. Lindsay AG. O’Donoghue AC. Smith AD. Chem. Commun.  2008,  3528 

9b Thomson JE. Rix K. Smith AD. Org. Lett.  2006,  8:  3785 

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 

10b Rendler S. Plefka O. Karatas B. Auer G. Fröhlich R. Mück-Lichtenfeld C. Grimme S. Oestreich M. Chem. Eur. J.  2008,  14:  11512 

10c Vedejs E. Jure M. Angew. Chem. Int. Ed.  2005,  44:  3974 

10d Miller SJ. Acc. Chem. Res.  2004,  37:  601 

11a Suzuki Y. Yamauchi K. Muramatsu K. Sato M. Chem Commun.  2004,  2770 

11b Kano T. Sasaki K. Maruoka K. Org. Lett.  2005,  7:  1347 

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

12b Zhu ZQ. Xiao JC. Adv. Synth. Catal.  2010,  352:  2455 

12c Kaeobamrung J. Mahatthananchai J. Zheng P. Bode JW. J. Am. Chem. Soc.  2010,  132:  8810 

12d Ryan SJ. Candish L. Lupton DW. J. Am. Chem. Soc.  2009,  131:  14176 

For NHC-catalyzed transesterifications, see:

13a Grasa GA. Güveli T. Singh R. Nolan SP. J. Org. Chem.  2003,  68:  2812 

13b Nyce GW. Lamboy JA. Connor EF. Waymouth RM. Hedrick JL. Org. Lett.  2002,  4:  3587 

14a De Sarkar S. Studer A. Org. Lett.  2010,  12:  1992 

14b De Sarkar S. Grimme S. Studer A. J. Am. Chem. Soc.  2010,  132:  1190 

14c Guin J. De Sarkar S. Grimme S. Studer A. Angew. Chem. Int. Ed.  2008,  47:  8727 ; Angew. Chem. 2008, 120, 8855

15

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

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 

17 Enders D. Niemeier O. Balensiefer T. Angew. Chem. Int. Ed.  2006,  45:  1463 

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.

19 Brand JP. Siles JIO. Waser J. Synlett  2010,  881 

20 Struble JR. Bode JW. Org. Synth.  2010,  87:  362 

21 Vora HU. Lathrop SP. Reynolds NT. Kerr MS. deAlaniz JR. Rovis T. Org. Synth.  2010,  87:  350 

22 Mahatthananchai J. Zheng P. Bode JW. Angew. Chem. Int. Ed.  2011,  50:  1673 

23 Kagan HB. Fiaud JC. Top. Stereochem.  1988,  18:  249 

24 Tietze LF. Kinzel T. Wolfram T. Chem. Eur. J.  2009,  15:  6199 

25 Luo Y. Herndon JW. Cervantes-Lee F. J. Am. Chem. Soc.  2003,  125:  12720 

26 Ryu E.-H. Cho HK. Zhao Y. Org. Lett.  2007,  9:  5147 

27 Belletire JL. Bills RA. Shackelford SA. Synth. Commun.  2008,  38:  738 

28 Enders D. Han J. Henseler A. Chem. Commun.  2008,  3989 

29 Chênevert R. Pelchat N. Morin P. Tetrahedron: Asymmetry  2009,  20:  1191