Diastereoselective nickel-catalyzed reductive aldol cyclizations using diethylzinc as the stoichiometric reductant: Scope and mechanistic insight

Pekka M. Joensuu, Gordon J. Murray, Euan. A. F. Fordyce, Thomas Luebbers, Hon Wai Lam

Research output: Contribution to journalArticlepeer-review

Abstract

In the presence of diethylzinc as a stoichiometric reductant, Ni(acac)(2) functions as an efficient. precatalyst for the reductive aldol cyclization of alpha,beta-unsaturated carbonyl compounds tethered to a ketone electrophile through an amide or an ester linkage. The reactions are tolerant of a wide range of substitution at both alpha,beta-unsaturated carbonyl and ketone components and proceed smoothly to furnish beta-hydroxylactams and beta-hydroxylactones with generally high diastereoselectivities. A series of experiments, including deuterium-labeling studies, was carried out in an attempt to gain some insight into the possible reaction mechanisms that might be operative.

Original languageEnglish
Pages (from-to)7328-7338
Number of pages11
JournalJournal of the American Chemical Society
Volume130
Issue number23
DOIs
Publication statusPublished - 11 Jun 2008

Keywords

  • ENANTIOSELECTIVE CONJUGATE ADDITION
  • OXIDATIVE CYCLIZATION
  • COUPLING REACTIONS
  • ALPHA,BETA-UNSATURATED ESTERS
  • CARBONYL-COMPOUNDS
  • BOND FORMATION
  • ALDEHYDES
  • HOMOALLYLATION
  • ALKYNES
  • ENONES

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