Formation of Three New Bonds and Two Stereocenters in Acyclic Systems by Zinc-Mediated Enantioselective Alkynylation of Acylsilanes, Brook Rearrangement, and Ene-Allene Carbocyclization Reactions

Polina Smirnov, Einat Katan, Jomon Mathew, Arseni Kostenko, Miriam Karni, Anne Nijs, Carsten Bolm, Yitzhak Apeloig, Ilan Marek

Research output: Contribution to journalArticlepeer-review

Abstract

Diastereoisomerically pure (dr > 99:1) and enantiomerically enriched (er up to 98:2) substituted propargyl diols possessing a tertiary hydroxyl group were synthesized in a single-pot operation from simple acylsilanes through a combined catalytic enantioselective alkynylation of acylsilanes, followed by an allenyl-Zn-Brook rearrangement and Zn-ene-allene (or Zn-yne-allene) cyclization reaction. Two remarkable features of these reactions are the near complete transfer of chirality in the allenyl-Zn-Brook rearrangement and the highly organized six-membered transition state of the Zn-ene-allene carbocyclization found by DFT calculations. In this process, three new bonds and two new stereogenic centers are created in a single-pot operation in excellent diastereo- and enantiomeric ratios. DFT calculations show that the allenyl-Zn-Brook rearrangement occurs in preference to the classic [1,2]-Zn-Brook rearrangement owing to its significantly lower activation barrier.

Original languageEnglish
Pages (from-to)12122-12135
Number of pages14
JournalJournal of Organic Chemistry
Volume79
Issue number24
DOIs
StatePublished - 19 Dec 2014

All Science Journal Classification (ASJC) codes

  • Organic Chemistry

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