Diastereo- and enantioselective conjugate addition of 3-substituted oxindoles to nitroolefins catalyzed by a chiral Ni(OAc)2-diamine complex under mild conditions.

A simple catalyst system assembled from an enantiomerically pure diamine ligand and Ni(OAc)(2) efficiently generates chiral metal enolates derived from 3-substituted oxindoles bearing an N-1 carbonyl group. The enolates smoothly undergo diastereo- and enantioselective conjugate addition to a wide range of nitroolefins under mild reaction conditions, furnishing 3,3-disubstituted oxindole products bearing two vicinal quaternary/tertiary stereocenters in 74-95% yields and 60:40 to 99:1 dr, 71-97% ee.

[1]  Xiaomei Zhang,et al.  Thiourea‐Catalyzed Highly Diastereo‐ and Enantioselective Conjugate Additions of α‐Substituted Cyanoacetates to Maleimides: Efficient Construction of Vicinal Quaternary‐ Tertiary Stereocenters , 2011 .

[2]  Xiaomei Zhang,et al.  Enantioselective 1,6-Michael addition of anthrone to 3-methyl-4-nitro-5-alkenyl-isoxazoles catalyzed by bifunctional thiourea-tertiary amines , 2011 .

[3]  Xiaomei Zhang,et al.  Amino-indanol-catalyzed asymmetric Michael additions of oxindoles to protected 2-amino-1-nitroethenes for the synthesis of 3,3'-disubstituted oxindoles bearing α,β-diamino functionality. , 2011, The Journal of organic chemistry.

[4]  Lin-feng Cun,et al.  Organocatalytic direct asymmetric aldol reactions of 3-isothiocyanato oxindoles to ketones: stereocontrolled synthesis of spirooxindoles bearing highly congested contiguous tetrasubstituted stereocenters. , 2011, Organic letters.

[5]  Xiaomei Zhang,et al.  Organocatalytic enantioselective hydroxymethylation of oxindoles with paraformaldehyde as C1 unit. , 2010, The Journal of organic chemistry.

[6]  Jian Zhou,et al.  Organocatalytic Michael addition of unprotected 3-substituted oxindoles to nitroolefins. , 2010, Organic & biomolecular chemistry.

[7]  Xiaomei Zhang,et al.  Highly enantioselective construction of spiro[4H-pyran-3,3'-oxindoles] through a domino Knoevenagel/Michael/cyclization sequence catalyzed by cupreine. , 2010, Organic letters.

[8]  Xiaomei Zhang,et al.  Highly diastereo- and enantioselective Michael additions of 3-substituted oxindoles to maleimides catalyzed by chiral bifunctional thiourea-tertiary amine. , 2010, Organic letters.

[9]  Jian Zhou,et al.  Catalytic Asymmetric Synthesis of Oxindoles Bearing a Tetrasubstituted Stereocenter at the C‐3 Position , 2010 .

[10]  Xiaomei Zhang,et al.  Organocatalytic Asymmetric Michael Addition of Pyrazolin-5-ones to Nitroolefins with Bifunctional Thiourea: Stereocontrolled Construction of Contiguous Quaternary and Tertiary Stereocenters , 2010 .

[11]  M. Sodeoka,et al.  Diastereo- and enantioselective conjugate addition of alpha-ketoesters to nitroalkenes catalyzed by a chiral Ni(OAc)(2) complex under mild conditions. , 2010, Journal of the American Chemical Society.

[12]  Bo Zhang,et al.  Asymmetric Michael Addition Reaction of 3‐Substituted Oxindoles to Nitroolefins Catalyzed by a Chiral Alkyl‐ Substituted Thiourea Catalyst , 2010 .

[13]  Xiaomei Zhang,et al.  Highly enantioselective aldol reaction of acetaldehyde and isatins only with 4-hydroxydiarylprolinol as catalyst: concise stereoselective synthesis of (R)-convolutamydines B and E, (−)-donaxaridine and (R)-chimonamidine , 2010 .

[14]  K. Maruoka,et al.  Enantioselective base-free phase-transfer reaction in water-rich solvent. , 2009, Journal of the American Chemical Society.

[15]  Xiaomei Zhang,et al.  Enantioselective Michael addition of anthrone to nitroalkenes catalyzed by bifunctional thiourea-tertiary amines , 2009 .

[16]  Q. Wei,et al.  Organocatalytic synthesis of spiro[pyrrolidin-3,3'-oxindoles] with high enantiopurity and structural diversity. , 2009, Journal of the American Chemical Society.

[17]  B. Trost,et al.  Asymmetric Syntheses of Oxindoleand Indole Spirocyclic Alkaloid Natural Products , 2009 .

[18]  S. Matsunaga,et al.  A homodinuclear Mn(III)2-Schiff base complex for catalytic asymmetric 1,4-additions of oxindoles to nitroalkenes. , 2009, Journal of the American Chemical Society.

[19]  C. Barbas,et al.  Thiourea-catalyzed highly enantio- and diastereoselective additions of oxindoles to nitroolefins: application to the formal synthesis of (+)-physostigmine. , 2009, Journal of the American Chemical Society.

[20]  Y. Takemoto,et al.  Enantioselective synthesis of 3,3-disubstituted oxindoles through Pd-catalyzed cyanoamidation. , 2008, Organic letters.

[21]  K. Scheidt,et al.  Pyrrolidinyl-spirooxindole natural products as inspirations for the development of potential therapeutic agents. , 2007, Angewandte Chemie.

[22]  N. Shibata,et al.  Cinchona-alkaloid-catalyzed enantioselective direct aldol-type reaction of oxindoles with ethyl trifluoropyruvate. , 2007, Angewandte Chemie.

[23]  B. Trost,et al.  Mo-catalyzed regio-, diastereo-, and enantioselective allylic alkylation of 3-aryloxindoles. , 2007, Journal of the American Chemical Society.

[24]  R. Matsubara,et al.  Catalytic asymmetric Michael reactions with enamides as nucleophiles. , 2007, Angewandte Chemie.

[25]  Davidr . Evans,et al.  Scope and mechanism of enantioselective Michael additions of 1,3-dicarbonyl compounds to nitroalkenes catalyzed by nickel(II)-diamine complexes. , 2007, Journal of the American Chemical Society.

[26]  R. Matsubara,et al.  Catalytic asymmetric amination of enecarbamates. , 2006, Angewandte Chemie.

[27]  R. Matsubara,et al.  Catalytic enantioselective and diastereoselective addition of aldehyde-derived enecarbamates to alpha-oxo aldehydes. , 2006, Angewandte Chemie.

[28]  B. Trost,et al.  Molybdenum-catalyzed asymmetric allylation of 3-alkyloxindoles: application to the formal total synthesis of (-)-physostigmine. , 2006, Journal of the American Chemical Society.

[29]  R. Matsubara,et al.  Copper(II)-catalyzed highly enantioselective addition of enamides to imines: the use of enamides as nucleophiles in asymmetric catalysis. , 2004, Angewandte Chemie.

[30]  L. Overman,et al.  The asymmetric intramolecular Heck reaction in natural product total synthesis. , 2003, Chemical reviews.

[31]  E. Carreira,et al.  Construction of Spiro[pyrrolidine‐3,3′‐oxindoles] − Recent Applications to the Synthesis of Oxindole Alkaloids , 2003 .

[32]  L. Overman,et al.  Catalytic asymmetric synthesis of quaternary carbons bearing two aryl substituents. Enantioselective synthesis of 3-alkyl-3-aryl oxindoles by catalytic asymmetric intramolecular heck reactions. , 2003, Journal of the American Chemical Society.

[33]  S. Danishefsky,et al.  Gelsemine: a thought-provoking target for total synthesis. , 2003, Angewandte Chemie.

[34]  Â. Pinto,et al.  The chemistry of isatins: a review from 1975 to 1999 , 2001 .