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Synlett 2011(19): 2761-2765  
DOI: 10.1055/s-0031-1289871
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© 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;
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Publication History

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

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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.

Key words

nickel - palladium - cross-coupling - asymmetric catalysis - stereoselective synthesis

    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 
    Search in Google Scholar
  • For reviews of alkyl cross-coupling reactions, see:
  • 2a Jana R. Pathak TP. Sigman MS. Chem. Rev.  2011,  111:  1417 
    Search in Google Scholar
  • 2b Rudolph A. Lautens M. Angew. Chem. Int. Ed.  2009,  48:  2656 
    Search in Google Scholar
  • 2c Frisch AC. Beller M. Angew. Chem. Int. Ed.  2005,  44:  674 
    Search in Google Scholar
  • 3a For a review of nickel-catalyzed methods, see: Netheton MR. Fu GC. Adv. Synth. Catal.  2004,  346:  1525 
    Search in Google Scholar
  • 3b For a review of palladium-catalyzed methods, see: Netherton MR. Fu GC. Top. Organomet. Chem.  2005,  14:  85 
    Search in Google Scholar
  • 4 For a previous review of asymmetric cross-coupling reactions of secondary alkyl halides, see: Glorius F. Angew. Chem. Int. Ed.  2008,  47:  8347 
    Search in Google Scholar
  • 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 
    Search in Google Scholar
  • 5c Boudier A. Darcel C. Flachsmann F. Micouin L. Oestreich M. Knochel P. Chem. Eur. J.  2000,  6:  2748 
    Search in Google Scholar
  • 5d Imao D. Glasspoole BW. Laberge VS. Crudden CM. J. Am. Chem. Soc.  2009,  131:  5024 
    Search in Google Scholar
  • 5e Ohmura T. Awano T. Suginome M. J. Am. Chem. Soc.  2010,  132:  13191 
    Search in Google Scholar
  • 5f Sandrock DL. Jean-Gérard L. Chen C. Dreher SD. Molander GA. J. Am. Chem. Soc.  2010,  132:  17108 
    Search in Google Scholar
  • 6 Arp FO. Fu GC. J. Am. Chem. Soc.  2005,  127:  10482 
    Search in Google Scholar
  • 7 Taylor BLH. Swift EC. Waetzig JD. Jarvo ER. J. Am. Chem. Soc.  2011,  133:  389 
    Search in Google Scholar
  • 8 Stille JK. Cowell AB. J. Organomet. Chem.  1977,  124:  253 
    Search in Google Scholar
  • 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 
    Search in Google Scholar
  • 10 For computational data that support the radical oxidative addition mechanism, see: Lin X. Phillips DL. J. Org. Chem.  2008,  73:  3680 
    Search in Google Scholar
  • 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 
    Search in Google Scholar
  • 12b Lou S. Fu GC. J. Am. Chem. Soc.  2010,  132:  1264 
    Search in Google Scholar
  • 12 Saito B. Fu GC. J. Am. Chem. Soc.  2008,  130:  6694 
    Search in Google Scholar
  • 13 Owston NA. Fu GC. J. Am. Chem. Soc.  2010,  132:  11908 
    Search in Google Scholar
  • 14 Zhe L. Wilsily A. Fu GC. J. Am. Chem. Soc.  2011,  133:  8154 
    Search in Google Scholar
  • 15 For a lead reference, see: Lipshutz BH. Wilhelm RS.
    J. Am. Chem. Soc.  1982,  104:  4696 
    Search in Google Scholar
  • 16 Legros J.-Y. Toffano M. Fiaud J.-C. Tetrahedron  1995,  51:  3235 
    Search in Google Scholar
  • 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 
    Search in Google Scholar
  • 17b Denmark SE. Burk MT. Hoover AJ. J. Am. Chem. Soc.  2010,  132:  1232 
    Search in Google Scholar
  • 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 
    Search in Google Scholar
  • 18b For a related mechanistic study, see: Assié M. Meddour A. Fiaud J.-C. Legros J.-Y. Tetrahedron: Asymmetry  2010,  21:  1701 
    Search in Google Scholar
  • 19 He A. Falck JR. J. Am. Chem. Soc.  2010,  132:  2524 
    Search in Google Scholar
  • 20a For related stereospecific reactions of α-hydroxy ester triflates, see: Studte C. Breit B. Angew. Chem. Int. Ed.  2008,  47:  5451 
    Search in Google Scholar
  • 20b For reactions of α-bromo arylsulfoxides, see: Rodrígues N. de Arellano CR. Asensio G. Medio-Simón M. Chem. Eur. J.  2007,  13:  4223 
    Search in Google Scholar
  • 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 
    Search in Google Scholar
  • 21b Kuwano R. Kondo Y. Org. Lett.  2004,  6:  3545 
    Search in Google Scholar
  • 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 
    Search in Google Scholar
  • 24b Beaton G, Moree WJ, Jovic F, Coon T, and Yu J. inventors; US Patent 11,156,252, Jan  19. 
  • 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.