The stereocontrolled total synthesis of spirastrellolide A methyl ester. Expedient construction of the key fragments

Org Biomol Chem. 2012 Aug 14;10(30):5861-72. doi: 10.1039/c2ob25100k. Epub 2012 Apr 16.

Abstract

Due to a combination of their promising anticancer properties, limited supply from the marine sponge source and their unprecedented molecular architecture, spirastrellolides represent attractive and challenging synthetic targets. A modular strategy for the synthesis of spirastrellolide A methyl ester, which allowed for the initial stereochemical uncertainties in the assigned structure was adopted, based on the envisaged sequential coupling of a series of suitably functionalised fragments; in this first paper, full details of the synthesis of these fragments are described. The pivotal C26-C40 DEF bis-spiroacetal was assembled by a double Sharpless asymmetric dihydroxylation/acetalisation cascade process on a linear diene intermediate, configuring the C31 and C35 acetal centres under suitably mild acidic conditions. A C1-C16 alkyne fragment was constructed by application of an oxy-Michael reaction to introduce the A-ring tetrahydropyran, a Sakurai allylation to install the C9 hydroxyl, and a 1,4-syn boron aldol/directed reduction sequence to establish the C11 and C13 stereocentres. Two different coupling strategies were investigated to elaborate the C26-C40 DEF fragment, involving either a C17-C25 sulfone or a C17-C24 vinyl iodide, each of which was prepared using an Evans glycolate aldol reaction. The remaining C43-C47 vinyl stannane fragment required for introduction of the unsaturated side chain was prepared from (R)-malic acid.

Publication types

  • Research Support, Non-U.S. Gov't

MeSH terms

  • Alkynes / chemistry
  • Chemistry Techniques, Synthetic
  • Kinetics
  • Macrolides / chemical synthesis*
  • Macrolides / chemistry*
  • Spiro Compounds / chemistry
  • Stereoisomerism
  • Substrate Specificity
  • Tin Compounds / chemistry
  • Vinyl Compounds / chemistry

Substances

  • Alkynes
  • Macrolides
  • Spiro Compounds
  • Tin Compounds
  • Vinyl Compounds
  • spirastrellolide A
  • vinyl iodide
  • stannane