Reductive aldol cyclizations of unsaturated thioester derivatives of 1,3-cyclopentanedione catalyzed by chiral copper hydrides

Jun Ou, Wing Tak Wong, Pauline Chiu

Research output: Journal article publicationJournal articleAcademic researchpeer-review

27 Citations (Scopus)

Abstract

The first study on the asymmetric reductive aldol reactions of enethioate derivatives of 1,3-cyclopentanedione showed that 5 mol % of TANIAPHOS (SL-T001-1), and Cu(OAc)2·H2O, together with phenylsilane as the stoichiometric reductant, generated the best yields and enantioselectivities of β-hydroxythioester products. With S-benzyl keto-enethioate as substrate, the bicyclo[4.3.0] hydroxythioester product was obtained only as the all-cis diastereomer, in good yield (84%) and enantioselectivity (up to 90% ee). With the related indanedione enethioate derivatives, the reductive aldol cyclization could attain up to 96% ee. These results demonstrate that enethioates have a significantly different reactivity and selectivity profile compared to enoate derivatives in the copper-catalyzed reductive aldol cyclization.
Original languageEnglish
Pages (from-to)3450-3456
Number of pages7
JournalTetrahedron
Volume68
Issue number17
DOIs
Publication statusPublished - 29 Apr 2012
Externally publishedYes

Keywords

  • Aldol reaction
  • Copper
  • Cyclization
  • Enantioselective catalysis
  • Reduction

ASJC Scopus subject areas

  • Biochemistry
  • Drug Discovery
  • Organic Chemistry

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