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Catalysis of 3-Pyrrolidinecarboxylic Acid and Related Pyrrolidine Derivatives in Enantioselective anti-Mannich-Type Reactions: Importance of the 3-Acid Group on Pyrrolidine for Stereocontrol

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Haile Zhang,^† Susumu Mitsumori,^† Naoto Utsumi,^† Masanori Imai,^† Noemi Garcia-Delgado,^† Maria Mifsud,^† Klaus Albertshofer,^† Paul Ha-Yeon Cheong,^§ K. N. Houk,^§ Fujie Tanaka,*^† and Carlos F. Barbas, III*^†;

The Skaggs Institute for Chemical Biology and the Departments of Chemistry and Molecular Biology, The Scripps Research Institute, 10550 North Torrey Pines Road, La Jolla, California 92037, and Department of Chemistry and Biochemistry, University of California, Los Angeles, California 90095-1569

J. Am. Chem. Soc., 2008, 130 (3), pp 875–886

DOI: 10.1021/ja074907+

Publication Date (Web): December 29, 2007

Section:

Physical Organic Chemistry

Abstract

The development of enantioselective anti-selective Mannich-type reactions of aldehydes and ketones with imines catalyzed by 3-pyrrolidinecarboxylic acid and related pyrrolidine derivatives is reported in detail. Both (3R,5R)-5-methyl-3-pyrrolidinecarboxylic acid and (R)-3-pyrrolidinecarboxylic acid efficiently catalyzed the reactions of aldehydes with α-imino esters under mild conditions and afforded anti-Mannich products with high diastereo- and enantioselectivities (anti/syn up to 99:1, up to >99% ee). For the reactions of ketones with α-imino esters, (R)-3-pyrrolidinecarboxylic acid was an efficient catalyst (anti/syn up to >99:1, up to 99% ee). Evaluation of a series of pyrrolidine-based catalysts indicated that the acid group at the β-position of the pyrrolidine ring of the catalyst played an important role in forwarding the carbon−carbon bond formation and in directing anti-selectivity and enantioselectivity.

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This article has been cited by 14 ACS Journal articles (5 most recent appear below).

Asymmetric Michael Addition of Malonates to Enones Catalyzed by a Primary β-Amino Acid and Its Lithium Salt
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The Journal of Organic Chemistry2011 76 (20), 8513-8517
- Asymmetric Michael Addition of Malonates to Enones Catalyzed by a Primary β-Amino Acid and Its Lithium Salt
  Masanori Yoshida, Mao Narita, and Shoji Hara
  The Journal of Organic Chemistry2011 76 (20), 8513-8517
  Highly enantioselective Michael addition of malonates to enones was achieved using a mixed catalyst consisting of a primary β-amino acid, O-TBDPS (S)-β-homoserine, and its lithium salt. Various cyclic and acyclic enones were converted into 1,5-ketoesters ...
  Abstract | Full Text HTML | Hi-Res PDF | PDF w/ Links
Quantum Mechanical Investigations of Organocatalysis: Mechanisms, Reactivities, and Selectivities
Paul Ha-Yeon Cheong, Claude Y. Legault, Joann M. Um, Nihan Çelebi-Ölçüm, and K. N. Houk
Chemical Reviews2011 111 (8), 5042-5137
- Quantum Mechanical Investigations of Organocatalysis: Mechanisms, Reactivities, and Selectivities
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  Chemical Reviews2011 111 (8), 5042-5137
  Abstract | Full Text HTML | Hi-Res PDF | PDF w/ Links
Catalytic Enantioselective Formation of C−C Bonds by Addition to Imines and Hydrazones: A Ten-Year Update
Shu̅ Kobayashi, Yuichiro Mori, John S. Fossey, and Matthew M. Salter
Chemical Reviews2011 111 (4), 2626-2704
- Catalytic Enantioselective Formation of C−C Bonds by Addition to Imines and Hydrazones: A Ten-Year Update
  Shu̅ Kobayashi, Yuichiro Mori, John S. Fossey, and Matthew M. Salter
  Chemical Reviews2011 111 (4), 2626-2704
  Abstract | Full Text HTML | Hi-Res PDF | PDF w/ Links
Development of the Ireland−Claisen Rearrangement of Alkoxy- and Aryloxy-Substituted Allyl Glycinates
James P. Tellam and David R. Carbery
The Journal of Organic Chemistry2010 75 (22), 7809-7821
- Development of the Ireland−Claisen Rearrangement of Alkoxy- and Aryloxy-Substituted Allyl Glycinates
  James P. Tellam and David R. Carbery
  The Journal of Organic Chemistry2010 75 (22), 7809-7821
  The Ireland−Claisen rearrangement of 3-alkoxy- and 3-aryloxy-substituted allyl glycinates is presented. This [3,3]-sigmatropic rearrangement route offers direct access to syn β-alkoxy and β-aryloxy α-amino acid systems. In particular, N,N-diboc glycine ...
  Abstract | Full Text HTML | Hi-Res PDF | PDF w/ Links
Highly Enantio- and Diastereoselective Mannich Reactions of Glycine Schiff Bases with in situ Generated N-Boc-imines Catalyzed by a Cinchona Alkaloid Thiourea
Haile Zhang, Salahuddin Syed and Carlos F. Barbas, III
Organic Letters2010 12 (4), 708-711
- Highly Enantio- and Diastereoselective Mannich Reactions of Glycine Schiff Bases with in situ Generated N-Boc-imines Catalyzed by a Cinchona Alkaloid Thiourea
  Haile Zhang, Salahuddin Syed and Carlos F. Barbas, III
  Organic Letters2010 12 (4), 708-711
  Highly enantio- and diastereoselective organocatalytic Mannich reactions of glycine Schiff bases with N-Boc-protected imines are described. Imines were generated in situ from bench-stable α-amido sulfones. Catalysis mediated by a cinchona alkaloid ...
  Abstract | Full Text HTML | Hi-Res PDF | PDF w/ Links

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Published In Issue January 23, 2008
Received July 3, 2007

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Article

Catalysis of 3-Pyrrolidinecarboxylic Acid and Related Pyrrolidine Derivatives in Enantioselective anti-Mannich-Type Reactions: Importance of the 3-Acid Group on Pyrrolidine for Stereocontrol

Abstract

Citing Articles

Asymmetric Michael Addition of Malonates to Enones Catalyzed by a Primary β-Amino Acid and Its Lithium Salt

Asymmetric Michael Addition of Malonates to Enones Catalyzed by a Primary β-Amino Acid and Its Lithium Salt

Quantum Mechanical Investigations of Organocatalysis: Mechanisms, Reactivities, and Selectivities

Quantum Mechanical Investigations of Organocatalysis: Mechanisms, Reactivities, and Selectivities

Catalytic Enantioselective Formation of C−C Bonds by Addition to Imines and Hydrazones: A Ten-Year Update

Catalytic Enantioselective Formation of C−C Bonds by Addition to Imines and Hydrazones: A Ten-Year Update

Development of the Ireland−Claisen Rearrangement of Alkoxy- and Aryloxy-Substituted Allyl Glycinates

Development of the Ireland−Claisen Rearrangement of Alkoxy- and Aryloxy-Substituted Allyl Glycinates

Highly Enantio- and Diastereoselective Mannich Reactions of Glycine Schiff Bases with in situ Generated N-Boc-imines Catalyzed by a Cinchona Alkaloid Thiourea

Highly Enantio- and Diastereoselective Mannich Reactions of Glycine Schiff Bases with in situ Generated N-Boc-imines Catalyzed by a Cinchona Alkaloid Thiourea

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