Synlett 2011(19): 2761-2765  
DOI: 10.1055/s-0031-1289871
SYNPACTS
© Georg Thieme Verlag Stuttgart ˙ New York

Construction of Enantioenriched Tertiary Stereogenic Centers by Nickel- and Palladium-Catalyzed Cross-Coupling Reactions of Alkyl Electrophiles

Buck L. H. Taylor, Elizabeth R. Jarvo*
Natural Sciences I 4114, Department of Chemistry, University of California, Irvine, CA 92697, USA
Fax: +1(949)8248571; e-Mail: erjarvo@uci.edu;
Further Information

Publication History

Received 11 July 2011
Publication Date:
11 November 2011 (online)

Abstract

Nickel and palladium catalysts have been developed for the cross-coupling of many challenging secondary alkyl electrophiles. Recent progress in this area is reviewed with emphasis on the control of stereochemistry in the formation of tertiary stereocenters. Stereoconvergent methods are discussed and recent alternative stereospecific approaches are highlighted.

    References and Notes

  • 1a Metal-Catalyzed Cross-Coupling Reactions   2nd ed.:  de Meijere A. Diederich F. Wiley-VCH; Weinheim: 2004. 
  • 1b Magano J. Dunetz JR. Chem. Rev.  2011,  111:  2177 
  • For reviews of alkyl cross-coupling reactions, see:
  • 2a Jana R. Pathak TP. Sigman MS. Chem. Rev.  2011,  111:  1417 
  • 2b Rudolph A. Lautens M. Angew. Chem. Int. Ed.  2009,  48:  2656 
  • 2c Frisch AC. Beller M. Angew. Chem. Int. Ed.  2005,  44:  674 
  • 3a For a review of nickel-catalyzed methods, see: Netheton MR. Fu GC. Adv. Synth. Catal.  2004,  346:  1525 
  • 3b For a review of palladium-catalyzed methods, see: Netherton MR. Fu GC. Top. Organomet. Chem.  2005,  14:  85 
  • 4 For a previous review of asymmetric cross-coupling reactions of secondary alkyl halides, see: Glorius F. Angew. Chem. Int. Ed.  2008,  47:  8347 
  • 5a

    For a review, see reference 2a.

  • 5b Hayashi T. Konishi M. Fukushima M. Mise T. Kagotani M. Tajika M. Kumada M. J. Am. Chem. Soc.  1982,  104:  180 
  • 5c Boudier A. Darcel C. Flachsmann F. Micouin L. Oestreich M. Knochel P. Chem. Eur. J.  2000,  6:  2748 
  • 5d Imao D. Glasspoole BW. Laberge VS. Crudden CM. J. Am. Chem. Soc.  2009,  131:  5024 
  • 5e Ohmura T. Awano T. Suginome M. J. Am. Chem. Soc.  2010,  132:  13191 
  • 5f Sandrock DL. Jean-Gérard L. Chen C. Dreher SD. Molander GA. J. Am. Chem. Soc.  2010,  132:  17108 
  • 6 Arp FO. Fu GC. J. Am. Chem. Soc.  2005,  127:  10482 
  • 7 Taylor BLH. Swift EC. Waetzig JD. Jarvo ER. J. Am. Chem. Soc.  2011,  133:  389 
  • 8 Stille JK. Cowell AB. J. Organomet. Chem.  1977,  124:  253 
  • For further experimental support for the radical oxidative addition mechanism, see:
  • 9a Jones GD. McFarland C. Anderson TJ. Vicic DA. J. Chem. Soc., Chem. Commun.  2005,  4211 
  • 9b Phapale VB. Buñuel E. García-Eglesias M. Cárdenas DJ. Angew. Chem. Int. Ed.  2007,  46:  8790 
  • 10 For computational data that support the radical oxidative addition mechanism, see: Lin X. Phillips DL. J. Org. Chem.  2008,  73:  3680 
  • For related, asymmetric nickel-catalyzed cross-couplings of racemic α-chloroamides and α-bromoketones, see:
  • 12a Lundin PM. Fu GC. J. Am. Chem. Soc.  2010,  132:  11027 
  • 12b Lou S. Fu GC. J. Am. Chem. Soc.  2010,  132:  1264 
  • 12 Saito B. Fu GC. J. Am. Chem. Soc.  2008,  130:  6694 
  • 13 Owston NA. Fu GC. J. Am. Chem. Soc.  2010,  132:  11908 
  • 14 Zhe L. Wilsily A. Fu GC. J. Am. Chem. Soc.  2011,  133:  8154 
  • 15 For a lead reference, see: Lipshutz BH. Wilhelm RS.
    J. Am. Chem. Soc.  1982,  104:  4696 
  • 16 Legros J.-Y. Toffano M. Fiaud J.-C. Tetrahedron  1995,  51:  3235 
  • The term enantiospecificity [% es = (product ee/starting material ee) × 100] has been used to describe the conser-vation of optical purity over the course of stereospecific transformations, see:
  • 17a Denmark SE. Vogler T. Chem. Eur. J.  2009,  15:  11737 
  • 17b Denmark SE. Burk MT. Hoover AJ. J. Am. Chem. Soc.  2010,  132:  1232 
  • 18a These results are consistent with k S>k R and moderate epimerization of the benzylpalladium complex (k rac ), see: Legros J.-Y. Boutros A. Fiaud J.-C. Toffano M.
    J. Mol. Catal. A: Chem.  2003,  196:  21 
  • 18b For a related mechanistic study, see: Assié M. Meddour A. Fiaud J.-C. Legros J.-Y. Tetrahedron: Asymmetry  2010,  21:  1701 
  • 19 He A. Falck JR. J. Am. Chem. Soc.  2010,  132:  2524 
  • 20a For related stereospecific reactions of α-hydroxy ester triflates, see: Studte C. Breit B. Angew. Chem. Int. Ed.  2008,  47:  5451 
  • 20b For reactions of α-bromo arylsulfoxides, see: Rodrígues N. de Arellano CR. Asensio G. Medio-Simón M. Chem. Eur. J.  2007,  13:  4223 
  • For cross-coupling reactions of benzylic ethers, see:
  • 21a Guan BT. Xiang SK. Wang BQ. Sun ZP. Wang Y. Zhao KQ. Shi ZJ. J. Am. Chem. Soc.  2008,  130:  3268 
  • 21b Kuwano R. Kondo Y. Org. Lett.  2004,  6:  3545 
  • 22 Takahashi T. Kanno K. Nickel-catalyzed Cross-coupling Reactions, In Modern Organonickel Chemistry   Tamaru Y. Wiley-VCH; Weinheim: 2005.  p.47 
  • 23 Comprehensive Asymmetric Catalysis   Vols. 1-3:  Jacobsen EN. Pfaltz A. Yamamoto H. Springer; Berlin: 1999. 
  • 24a Moree WJ. Li B.-F. Jovic F. Coon T. Yu J. Gross RS. Tucci F. Marinkovic D. Zamani-Kord S. Malany S. Bradbury MJ. Hernandez LM. O’Brien Z. Wen J. Wang H. Hoare SRJ. Petroski RE. Sacaan A. Madan A. Crowe PD. Beaton G. J. Med. Chem.  2009,  52:  5307 
  • 24b Beaton G, Moree WJ, Jovic F, Coon T, and Yu J. inventors; US Patent 11,156,252, Jan  19.  2006
  • 25 Alami M, Messaoudi S, Hamze A, Provot O, Brion J.-D, Liu J.-M, Bignon J, and Bakala J. inventors; Patent WO/2009/147217 A1, Dec  10.  2009