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Stereochemistry of the Intermolecular and Intramolecular Conjugate Additions of Amines and Anions to Chiral (E)- and (Z)-Vinyl Sulfoxides. Total Syntheses of (R )-( + )-Carnegine and ( + )- and (-)-Sedamine

Journal Article


Abstract


  • The intramolecular addition of incipient amine anions to chiral (E)- and (Z)-vinyl sulfoxides occurs in the same diastereofacial sense, giving chiral isoquinoline and piperidine derivatives that differ in relative stereochemistry at C-2. In contrast, the conjugate addition reactions of (E)- and (Z)-/?-styryl p-tolyl sulfoxide with benzylamine and LiCH(C02Et)2 are diastereoconvergent processes. The same major diastereomeric product is obtained in each case. We have attempted to rationalize the stereochemical outcome of the addition of nucleophiles to chiral vinyl sulfoxides according to the type of nucleophilic reagent employed (either chelating/hydrogen bonding or nonchelating) and from a consideration of possible transition states. © 1990, American Chemical Society. All rights reserved.

Publication Date


  • 1990

Citation


  • Pyne, S. G., Bloem, P., Chapman, S. L., Dixon, C. E., & Griffith, R. (1990). Stereochemistry of the Intermolecular and Intramolecular Conjugate Additions of Amines and Anions to Chiral (E)- and (Z)-Vinyl Sulfoxides. Total Syntheses of (R )-( + )-Carnegine and ( + )- and (-)-Sedamine. Journal of Organic Chemistry, 55(3), 1086-1093. doi:10.1021/jo00290a051

Scopus Eid


  • 2-s2.0-0025356814

Web Of Science Accession Number


Start Page


  • 1086

End Page


  • 1093

Volume


  • 55

Issue


  • 3

Abstract


  • The intramolecular addition of incipient amine anions to chiral (E)- and (Z)-vinyl sulfoxides occurs in the same diastereofacial sense, giving chiral isoquinoline and piperidine derivatives that differ in relative stereochemistry at C-2. In contrast, the conjugate addition reactions of (E)- and (Z)-/?-styryl p-tolyl sulfoxide with benzylamine and LiCH(C02Et)2 are diastereoconvergent processes. The same major diastereomeric product is obtained in each case. We have attempted to rationalize the stereochemical outcome of the addition of nucleophiles to chiral vinyl sulfoxides according to the type of nucleophilic reagent employed (either chelating/hydrogen bonding or nonchelating) and from a consideration of possible transition states. © 1990, American Chemical Society. All rights reserved.

Publication Date


  • 1990

Citation


  • Pyne, S. G., Bloem, P., Chapman, S. L., Dixon, C. E., & Griffith, R. (1990). Stereochemistry of the Intermolecular and Intramolecular Conjugate Additions of Amines and Anions to Chiral (E)- and (Z)-Vinyl Sulfoxides. Total Syntheses of (R )-( + )-Carnegine and ( + )- and (-)-Sedamine. Journal of Organic Chemistry, 55(3), 1086-1093. doi:10.1021/jo00290a051

Scopus Eid


  • 2-s2.0-0025356814

Web Of Science Accession Number


Start Page


  • 1086

End Page


  • 1093

Volume


  • 55

Issue


  • 3