Transition-metal-catalyzed cycloadditions for the synthesis of eight-membered carbocycles

Chem Asian J. 2010 May 3;5(5):1072-88. doi: 10.1002/asia.200900712.

Abstract

Eight-membered carbocycles are found in a wide variety of natural products that exhibit a broad range of biological and medicinal activities (cf. the most potent anticancer drug, taxol). However, the synthesis of eight-membered carbocycles is quite challenging as traditional approaches are met with entropic and enthalpic penalties in the ring-forming transition states. These negative effects can be totally or partially avoided with the implementation of transition-metal-catalyzed/mediated cycloadditions. In this Focus Review, examples of elegant and efficient metal-catalyzed and some metal-mediated cycloadditions (including Ni- catalyzed [4+4] and Rh-catalyzed [4+2+2] and [5+2+1] reactions) are presented to illustrate this. Application of these cycloaddition reactions in total synthesis is also presented to show the significance of these reactions in addressing challenges in natural product synthesis.

Publication types

  • Research Support, Non-U.S. Gov't
  • Review

MeSH terms

  • Catalysis
  • Cyclization
  • Cyclooctanes / chemical synthesis*
  • Cyclooctanes / chemistry
  • Polycyclic Sesquiterpenes
  • Sesquiterpenes / chemical synthesis
  • Sesquiterpenes / chemistry
  • Transition Elements / chemistry*

Substances

  • Cyclooctanes
  • Polycyclic Sesquiterpenes
  • Sesquiterpenes
  • Transition Elements
  • hirsutene
  • hypnophilin