Total Synthesis of β-Chamigrene

Author: Dow, William Clinton

Year: 1982

Degree: Dissertation (Ph.D.)

Advisor: Grubbs, Robert H.

Committee Members: Grubbs, Robert H.; Ireland, Robert E.; Anson, Fred C.; Dougherty, Dennis A.

Option: Chemistry

DOI: 10.7907/6kmn-mt31

Abstract

A total synthesis of the sesquiterpene (±)-β-Chamigrene is described. A key step is the preparation of spiroketone ii through Claisen rearrangement of the vinyl-substituted cycloheptapyran i. A modified Meinwald-Cava ring contraction sequence is used for the intramolecular elaboration of a functionalized one-carbon unit at the hindered alpha flank of the spirocycle. This procedure affords ester iii. Alternate reaction pathways available to the reactive ketene intermediate are also discussed. These results are compared with observations made in a previously reported synthesis of aphidicolin.

[Chemical structure included in scanned thesis' abstract, p. iv.]

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