Download PDF
Synlett 2011(20): 2907-2912  
DOI: 10.1055/s-0031-1289892
SYNPACTS
© Georg Thieme Verlag Stuttgart ˙ New York

Asymmetric Inverse-Electron-Demand Hetero-Diels-Alder Reaction via Enamine-Metal Lewis Acid Bifunctional Catalysis

Zhenghu Xu*a, Hong Wang*b
a Key Lab of Colloid and Interface Chemistry of Ministry of Education, School of Chemistry and Chemical Engineering, Shandong, University, No. 27 South Shanda Road, Jinan 250100, Shandong Province, P. R. of China
e-Mail: xuzh@sdu.edu.cn;
b Department of Chemistry and Biochemistry, Miami University, 254 Hughes Laboratories, 701 E High Street, Oxford, OH 45056, USA
Fax: +1(513)5295715; e-Mail: wangh3@muohio.edu;
Further Information

Publication History

Received 18 August 2011
Publication Date:
23 November 2011 (online)

    Permissions and Reprints All articles of this category

Abstract

This paper describes the development of an efficient and atom-economic asymmetric inverse-electron-demand hetero-­Diels-Alder reaction of six-membered ketones with β,γ-unsaturated α-keto esters via enamine-metal Lewis acid bifunctional catalysis.

Key words

asymmetric catalysis - bifunctional catalysis - enamines - Lewis acids - ketones - Hetero-Diels-Alder reaction

    References and Notes

  • 1a Pellissier H. Tetrahedron  2009,  65:  2839 
    Google Scholar
  • 1b Jorgensen KA. Eur. J. Org. Chem.  2004,  2093 
    Google Scholar
  • 1c Jorgensen KA. Johannsen M. Yao SL. Audrain H. Thorhauge J. Acc. Chem. Res.  1999,  32:  605 
    Google Scholar
  • 1d Alfini R. Cecchi M. Giomi D. Molecules  2010,  15:  1722 
    Google Scholar
  • 2a Juhl K. Jorgensen KA. Angew. Chem. Int. Ed.  2003,  42:  1498 
    Google Scholar
  • 2b Zhao Y. Wang XJ. Liu JT. Synlett  2008,  1017 
    Google Scholar
  • 2c Samanta S. Krause J. Mandal T. Zhao CG. Org. Lett.  2007,  9:  2745 
    Google Scholar
  • 2d Xie HX. Zu LS. Oueis HR. Wang HLJ. Wang W. Org. Lett.  2008,  10:  1923 
    Google Scholar
  • 2e Han B. He ZQ. Li JL. Li R. Jiang K. Liu TY. Chen YC. Angew. Chem. Int. Ed.  2009,  48:  5474 
    Google Scholar
  • 2f Han B. Li JL. Ma C. Zhang SJ. Chen YC. Angew. Chem. Int. Ed.  2008,  47:  9971 
    Google Scholar
  • 2g Wang J. Yu F. Zhang X. Ma D. Org. Lett.  2008,  10:  2561 
    Google Scholar
  • 3 Xu ZH. Liu L. Wheeler K. Wang H. Angew. Chem. Int. Ed.  2011,  50:  3484 
    Google Scholar
  • 4a Yanagisawa A. Arai T. Chem. Commun.  2008,  1165 
    Google Scholar
  • 4b Desimoni G. Faita G. Jorgensen KA. Chem. Rev.  2006,  106:  3561 
    Google Scholar
  • 4c Bartok M. Chem. Rev.  2010,  110:  1663 
    Google Scholar
  • 4d Jorgensen KA. Angew. Chem. Int. Ed.  2000,  39:  3558 
    Google Scholar
  • 5a Thorhauge J. Johannsen M. Jorgensen KA. Angew. Chem. Int. Ed.  1998,  37:  2404 
    Google Scholar
  • 5b Evans DA. Johnson JS. J. Am. Chem. Soc.  1998,  120:  4895 
    Google Scholar
  • 5c Evans DA. Olhava EJ. Johnson JS. Janey JM. Angew. Chem. Int. Ed.  1998,  37:  3372 
    Google Scholar
  • 5d Evans DA. Johnson JS. Olhava EJ. J. Am. Chem. Soc.  2000,  122:  1635 
    Google Scholar
  • 5e Jørgensen KA. Angew. Chem. Int. Ed.  2000,  39:  3558 
    Google Scholar
  • 5f Gademann K. Chavez DE. Jacobsen EN. Angew. Chem. Int. Ed.  2002,  41:  3059 
    Google Scholar
  • 6 Esquivias J. Arrayas RG. Carretero JC. J. Am. Chem. Soc.  2007,  129:  1480 
    Google Scholar
  • 7 Li P. Yamamoto H. J. Am. Chem. Soc.  2009,  131:  16628 
    Google Scholar
  • 8 Gallier F. Hussain H. Martel A. Kirschning A. Dujardin G. Org. Lett.  2009,  11:  3060 
    Google Scholar
  • 9a Zheng C. Wu Y. Wang X. Zhao G. Adv. Synth. Catal.  2008,  350:  2690 
    Google Scholar
  • 9b Cao CL. Sun XL. Kang YB. Tang Y. Org. Lett.  2007,  9:  4151 
    Google Scholar
  • For reviews, see
  • 10a Shao ZH. Zhang HB. Chem. Soc. Rev.  2009,  38:  2745 
    Google Scholar
  • 10b Zhong C. Shi XD. Eur. J. Org. Chem.  2010,  2999 
    Google Scholar
  • For examples, see:
  • 10c Allen AE. MacMillan DWC. J. Am. Chem. Soc.  2010,  132:  4986 
    Google Scholar
  • 10d Yang T. Ferrali A. Campbell L. Dixon DJ. Chem. Commun.  2008,  2923 
    Google Scholar
  • 10e Ding QP. Wu J. Org. Lett.  2007,  9:  4959 
    Google Scholar
  • 10f Ibrahem I. Cordova A. Angew. Chem. Int. Ed.  2006,  45:  1952 
    Google Scholar
  • 10g Bihelovic F. Matovic R. Vulovic B. Saicic RN. Org. Lett.  2007,  9:  5063 
    Google Scholar
  • 10h Usui I. Schmidt S. Breit B. Org. Lett.  2009,  11:  1453 
    Google Scholar
  • 10i Lin SZ. Zhao GL. Deiana L. Sun JL. Zhang QO. Leijonmarck H. Cordova A. Chem. Eur. J.  2010,  16:  13930 
    Google Scholar
  • 10j Hashmi ASK. Hubbert C. Angew. Chem. Int. Ed.  2010,  49:  1010 
    Google Scholar
  • 10k Binder JT. Crone B. Haug TT. Menz H. Kirsch SF. Org. Lett.  2008,  10:  1025 
    Google Scholar
  • 10l Ikeda M. Miyake Y. Nishibayashi Y. Angew. Chem. Int. Ed.  2010,  49:  7289 
    Google Scholar
  • 10m Abillard O. Breit B. Adv. Synth. Catal.  2007,  349:  1891 
    Google Scholar
  • 10n Chercheja S. Eilbracht P. Adv. Synth. Catal.  2007,  349:  1897 
    Google Scholar
  • 10o Quintard A. Alexakis A. Mazet C. Angew. Chem. Int. Ed.  2011,  50:  2354 
    Google Scholar
  • 10p Kemme ST. Smejkal T. Breit B. Chem. Eur. J.  2010,  16:  3423 
    Google Scholar
  • 10q Abillard O. Breit B. Adv. Synth. Catal.  2007,  349:  1891 
    Google Scholar
  • 10r Chercheja S. Eilbracht P. Adv. Synth. Catal.  2007,  349:  1897 
    Google Scholar
  • 10s Nicewicz DA. MacMillan DWC. Science  2008,  322:  77 
    Google Scholar
  • 10t Nagib DA. Scott ME. MacMillan DWC. J. Am. Chem. Soc.  2009,  131:  10875 
    Google Scholar
  • 12a Paull DH. Abraham CJ. Scerba MT. Alden-Danforth E. Lectka T. Acc. Chem. Res.  2008,  41:  655 
    Google Scholar
  • 12b Groger H. Chem. Eur. J.  2001,  7:  5247 
    Google Scholar
  • 12c Wu LY. Bencivenni G. Mancinelli M. Mazzanti A. Bartoli G. Melchiorre P. Angew. Chem. Int. Ed.  2009,  48:  7196 
    Google Scholar
  • 12d Kanai M. Kato N. Ichikawa E. Shibasaki M. Synlett  2005,  1491 
    Google Scholar
  • Although it was not clearly defined as enamine-metal Lewis acid bifunctional catalysts, the first example of the combination of an organo-amine catalyst with a metal salt through a chelating ligand was reported by the Mlynarski group. For details, see:
  • 13a Paradowska J. Stodulski M. Mlynarski J. Adv. Synth. Catal.  2007,  349:  1041 
    Google Scholar
  • 13b Pasternak M. Paradowska J. Rogozinska M. Mlynarski J. Tetrahedron Lett.  2010,  51:  4088 
    Google Scholar
  • 13c Mlynarski J. Paradowska J. Chem. Soc. Rev.  2008,  37:  1502 
    Google Scholar
  • 13d Paradowska J. Stodulski M. Mlynarski J. Angew. Chem. Int. Ed.  2009,  48:  4288 
    Google Scholar
  • 14a Xu ZH. Daka P. Wang H. Chem. Commun.  2009,  6825 
    Google Scholar
  • 14b Xu ZH. Daka P. Budik I. Wang H. Bai FQ. Zhang HX. Eur. J. Org. Chem.  2009,  4581 
    Google Scholar
  • 14c Daka P. Xu ZH. Alexa A. Wang H. Chem. Commun.  2011,  47:  224 
    Google Scholar
11

Other types of catalytic systems combining enamine catalysis with metal catalysis have also been reported recently. In these systems, the enamine catalysis and
the metal catalysis occur in sequence, see refs. 10o-t