Combined C−H Activation/Cope Rearrangement as a Strategic Reaction in Organic Synthesis:  Total Synthesis of (−)-Colombiasin A and (−)-Elisapterosin B

Huw M. L. Davies,* Xing Dai, and Matthew S. Long
Contribution from the Department of Chemistry, University at Buffalo, The State University of New York, Buffalo, New York 14260-3000
J. Am. Chem. Soc., 2006, 128 (7), pp 2485–2490
DOI: 10.1021/ja056877l
Publication Date (Web): January 31, 2006
Copyright © 2006 American Chemical Society
*

In papers with more than one author, the asterisk indicates the name of the author to whom inquiries about the paper should be addressed.

, hdavies@acsu.buffalo.edu

Abstract

Abstract Image

The total synthesis of (−)-colombiasin A (2) and (−)-elisapterosin B (3) has been achieved. The key step is a C−H functionalization process, the combined C−H activation/Cope rearrangement, between methyl (E)-2-diazo-3-pentenoate and 1-methyl-1,2-dihydronaphthalenes. When the reaction is catalyzed by dirhodium tetrakis((R)-(N-dodecylbenzenesulfonyl)prolinate), Rh2(R-DOSP)4, an enantiomer differentiation step occurs where one enantiomer of the dihydronaphthalene undergoes the combined C−H activation/Cope rearrangement while the other undergoes cyclopropanation. This sequence controls the three key stereocenters in the natural products such that the remainder of the synthesis is feasible using standard chemistry.

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History

  • Published In Issue February 22, 2006
  • Received October 7, 2005

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