A practical synthesis of (+)-discodermolide and analogues: fragment union by complex aldol reactions

J Am Chem Soc. 2001 Oct 3;123(39):9535-44. doi: 10.1021/ja011211m.

Abstract

A practical stereocontrolled synthesis of (+)-discodermolide (1) has been completed in 10.3% overall yield (23 steps longest linear sequence). The absolute stereochemistry of the C(1)-C(6) (7), C(9)-C(16) (8), and C(17)-C(24) (9) subunits was established via substrate-controlled, boron-mediated, aldol reactions of the chiral ethyl ketones 10, 11, and 12. Key fragment coupling reactions were a lithium-mediated, anti-selective, aldol reaction of aryl ester 8 (under Felkin-Anh induction from the aldehyde component 9), followed by in situ reduction to produce the 1,3-diol 40, and a (+)-diisopinocampheylboron chloride-mediated aldol reaction of methyl ketone 7 (overturning the inherent substrate induction from the aldehyde component 52) to give the (7S)-adduct 58. The flexibility of our overall strategy is illustrated by the synthesis of a number of diastereomers and structural analogues of discodermolide, which should serve as valuable probes for structure-activity studies.

Publication types

  • Research Support, Non-U.S. Gov't

MeSH terms

  • Aldehydes / chemistry*
  • Alkanes*
  • Antineoplastic Agents / chemical synthesis
  • Carbamates*
  • Immunosuppressive Agents / chemical synthesis
  • Lactones / chemical synthesis*
  • Pyrones
  • Stereoisomerism

Substances

  • Aldehydes
  • Alkanes
  • Antineoplastic Agents
  • Carbamates
  • Immunosuppressive Agents
  • Lactones
  • Pyrones
  • 3-hydroxybutanal
  • discodermolide