Desymmetrization and switching of stereoselectivity in direct organocatalytic Michael addition of ketones to 1,1-bis(phenylsulfonyl)ethylene

Yan Ming Chen, Pei Hsun Lee, Jun Lin, Kwunmin Chen

Research output: Contribution to journalArticle

14 Citations (Scopus)

Abstract

The organocatalytic desymmetrization was demonstrated for 4-substituted cyclohexanones by treatment with a vinyl sulfone in the presence of an organocatalyst. The desired Michael adducts were typically obtained in high chemical yields and high to excellent stereoselectivities (up to 97 % yield, 93 % ee). An efficient desymmetrization method was developed for the synthesis of enantiomeric products by using either camphor-derived pyrrolidine V or cinchonidine-derived primary amine VII as a catalyst. The absolute stereochemistry of the (2R,4R)-2-[2,2-bis(phenylsulfonyl)ethyl]-4- methylcyclohexanone (3a) and (2R,4R)-2-[2,2-bis(phenylsulfonyl)ethyl]-4-tert- butylcyclohexanone (3b) was confirmed by single-crystal X-ray structure analyses. The direct organocatalytic desymmetrization was demonstrated for 4-substituted cyclohexanones by treatment with a vinyl sulfone in CHCl 3. The desired Michael adducts were obtained in high chemical yields and stereoselectivities (up to 97 % yield, 93 % ee). Enantiomeric products were obtained by using either a camphor-derived pyrrolidine or a cinchonidine-derived primary amine as a catalyst.

Original languageEnglish
Pages (from-to)2699-2707
Number of pages9
JournalEuropean Journal of Organic Chemistry
Issue number13
DOIs
Publication statusPublished - 2013 May 1

Fingerprint

Cyclohexanones
Camphor
Stereoselectivity
Ketones
ketones
Amines
ethylene
camphor
Stereochemistry
Catalysts
sulfones
adducts
amines
Single crystals
catalysts
X rays
stereochemistry
products
divinyl sulfone
cinchonidine

Keywords

  • Asymmetric catalysis
  • Enantioselectivity
  • Michael addition
  • Organocatalysis
  • Synthetic methods

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Organic Chemistry

Cite this

Desymmetrization and switching of stereoselectivity in direct organocatalytic Michael addition of ketones to 1,1-bis(phenylsulfonyl)ethylene. / Chen, Yan Ming; Lee, Pei Hsun; Lin, Jun; Chen, Kwunmin.

In: European Journal of Organic Chemistry, No. 13, 01.05.2013, p. 2699-2707.

Research output: Contribution to journalArticle

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