Enantio- and Diastereoselective Synthesis of 1,5-syn-(Z)-Amino Alcohols via Imine Double Allylboration: Synthesis of trans-1,2,3,6-Tetrahydropyridines and Total Synthesis of Andrachcine

Org Lett. 2017 May 19;19(10):2646-2649. doi: 10.1021/acs.orglett.7b00995. Epub 2017 May 4.

Abstract

A stereoselective synthesis of trans-1,2,3,6-tetrahydropyridines 8 is described. This synthesis proceeds via intramolecular Mistunobu reactions of 1,5-syn-(Z)-amino alcohols 7, which were prepared by a highly diastereo- and enantioselective double-allylboration reaction of aldehyde 5 and silylimine 6. The chiral bifunctional γ-borylallylborane 9E was generated in situ by hydroboration of allene 3 with (diisopinocampheyl)borane 4. This strategy was applied to the total synthesis of andrachcine 1, thus establishing with certainty the absolute and relative configuration of the natural product.

Publication types

  • Research Support, N.I.H., Extramural

MeSH terms

  • Amino Alcohols / chemical synthesis*
  • Halogenation
  • Imines
  • Molecular Structure
  • Pyrrolidines
  • Stereoisomerism

Substances

  • Amino Alcohols
  • Imines
  • Pyrrolidines