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

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.

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

References and Notes

<A NAME="RP02011ST-1A">1a</A> Metal-Catalyzed Cross-Coupling Reactions   2nd ed.:  de Meijere A. Diederich F. Wiley-VCH; Weinheim: 2004. 

<A NAME="RP02011ST-1B">1b</A> Magano J. Dunetz JR. Chem. Rev.  2011,  111:  2177 

For reviews of alkyl cross-coupling reactions, see:

<A NAME="RP02011ST-2A">2a</A> Jana R. Pathak TP. Sigman MS. Chem. Rev.  2011,  111:  1417 

<A NAME="RP02011ST-2B">2b</A> Rudolph A. Lautens M. Angew. Chem. Int. Ed.  2009,  48:  2656 

<A NAME="RP02011ST-2C">2c</A> Frisch AC. Beller M. Angew. Chem. Int. Ed.  2005,  44:  674 

<A NAME="RP02011ST-3A">3a</A> For a review of nickel-catalyzed methods, see: Netheton MR. Fu GC. Adv. Synth. Catal.  2004,  346:  1525 

<A NAME="RP02011ST-3B">3b</A> For a review of palladium-catalyzed methods, see: Netherton MR. Fu GC. Top. Organomet. Chem.  2005,  14:  85 

<A NAME="RP02011ST-4">4</A> For a previous review of asymmetric cross-coupling reactions of secondary alkyl halides, see: Glorius F. Angew. Chem. Int. Ed.  2008,  47:  8347 

<A NAME="RP02011ST-5A">5a</A>

For a review, see reference 2a.

<A NAME="RP02011ST-5B">5b</A> Hayashi T. Konishi M. Fukushima M. Mise T. Kagotani M. Tajika M. Kumada M. J. Am. Chem. Soc.  1982,  104:  180 

<A NAME="RP02011ST-5C">5c</A> Boudier A. Darcel C. Flachsmann F. Micouin L. Oestreich M. Knochel P. Chem. Eur. J.  2000,  6:  2748 

<A NAME="RP02011ST-5D">5d</A> Imao D. Glasspoole BW. Laberge VS. Crudden CM. J. Am. Chem. Soc.  2009,  131:  5024 

<A NAME="RP02011ST-5E">5e</A> Ohmura T. Awano T. Suginome M. J. Am. Chem. Soc.  2010,  132:  13191 

<A NAME="RP02011ST-5F">5f</A> Sandrock DL. Jean-Gérard L. Chen C. Dreher SD. Molander GA. J. Am. Chem. Soc.  2010,  132:  17108 

<A NAME="RP02011ST-6">6</A> Arp FO. Fu GC. J. Am. Chem. Soc.  2005,  127:  10482 

<A NAME="RP02011ST-7">7</A> Taylor BLH. Swift EC. Waetzig JD. Jarvo ER. J. Am. Chem. Soc.  2011,  133:  389 

<A NAME="RP02011ST-8">8</A> Stille JK. Cowell AB. J. Organomet. Chem.  1977,  124:  253 

For further experimental support for the radical oxidative addition mechanism, see:

<A NAME="RP02011ST-9A">9a</A> Jones GD. McFarland C. Anderson TJ. Vicic DA. J. Chem. Soc., Chem. Commun.  2005,  4211 

<A NAME="RP02011ST-9B">9b</A> Phapale VB. Buñuel E. García-Eglesias M. Cárdenas DJ. Angew. Chem. Int. Ed.  2007,  46:  8790 

<A NAME="RP02011ST-10">10</A> 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:

<A NAME="RP02011ST-12A">12a</A> Lundin PM. Fu GC. J. Am. Chem. Soc.  2010,  132:  11027 

<A NAME="RP02011ST-12B">12b</A> Lou S. Fu GC. J. Am. Chem. Soc.  2010,  132:  1264 

<A NAME="RP02011ST-12">12</A> Saito B. Fu GC. J. Am. Chem. Soc.  2008,  130:  6694 

<A NAME="RP02011ST-13">13</A> Owston NA. Fu GC. J. Am. Chem. Soc.  2010,  132:  11908 

<A NAME="RP02011ST-14">14</A> Zhe L. Wilsily A. Fu GC. J. Am. Chem. Soc.  2011,  133:  8154 

<A NAME="RP02011ST-15">15</A> For a lead reference, see: Lipshutz BH. Wilhelm RS.
J. Am. Chem. Soc.  1982,  104:  4696 

<A NAME="RP02011ST-16">16</A> 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:

<A NAME="RP02011ST-17A">17a</A> Denmark SE. Vogler T. Chem. Eur. J.  2009,  15:  11737 

<A NAME="RP02011ST-17B">17b</A> Denmark SE. Burk MT. Hoover AJ. J. Am. Chem. Soc.  2010,  132:  1232 

<A NAME="RP02011ST-18A">18a</A> 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 

<A NAME="RP02011ST-18B">18b</A> For a related mechanistic study, see: Assié M. Meddour A. Fiaud J.-C. Legros J.-Y. Tetrahedron: Asymmetry  2010,  21:  1701 

<A NAME="RP02011ST-19">19</A> He A. Falck JR. J. Am. Chem. Soc.  2010,  132:  2524 

<A NAME="RP02011ST-20A">20a</A> For related stereospecific reactions of α-hydroxy ester triflates, see: Studte C. Breit B. Angew. Chem. Int. Ed.  2008,  47:  5451 

<A NAME="RP02011ST-20B">20b</A> 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:

<A NAME="RP02011ST-21A">21a</A> Guan BT. Xiang SK. Wang BQ. Sun ZP. Wang Y. Zhao KQ. Shi ZJ. J. Am. Chem. Soc.  2008,  130:  3268 

<A NAME="RP02011ST-21B">21b</A> Kuwano R. Kondo Y. Org. Lett.  2004,  6:  3545 

<A NAME="RP02011ST-22">22</A> Takahashi T. Kanno K. Nickel-catalyzed Cross-coupling Reactions, In Modern Organonickel Chemistry   Tamaru Y. Wiley-VCH; Weinheim: 2005.  p.47 

<A NAME="RP02011ST-23">23</A> Comprehensive Asymmetric Catalysis   Vols. 1-3:  Jacobsen EN. Pfaltz A. Yamamoto H. Springer; Berlin: 1999. 

<A NAME="RP02011ST-24A">24a</A> 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 

<A NAME="RP02011ST-24B">24b</A> Beaton G, Moree WJ, Jovic F, Coon T, and Yu J. inventors; US Patent 11,156,252, Jan  19. 

<A NAME="RP02011ST-25">25</A> 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.