The synthesis of phorbol C-ring analogs, a model study on the phorbol to 12-hydroxydaphnetoxin conversion, and other synthetic studies
Abstract
The synthesis of phorbol C-ring analogs is described. The results of a model study on the phorbol to 12-hydroxydaphnetoxin biomimetic conversion using a C-9 ester-assisted cyclopropyl carbinyl rearrangement are presented. The synthetic studies of phorbol C-ring analogs led to the development of a modified Kumada-Fleming strategy, in which use was made of allyldimethylsilyl group as a latent form of hydroxyl functionality. The scope and limitations of this methodology are described. The work on efficient generation and use of 3-phenylsulfonylcyclopentadienone as an activated Diels-Alder dienophile, is presented in Chapter four. Finally, a new preparation of homochiral cyclopentenylsulfones is described, wherein use has been made of (4+1) carbocyclization of a homochiral four-carbon piece (1,4-dihalide or ditriflate) with an activated methylene unit (phenylsulfonyl trifluoromethylsulfonyl methane). The activating and leaving capabilities of triflone group in cycloalkylation and subsequent directed 1,2-eliminations are examined.
Degree
Ph.D.
Advisors
Fuchs, Purdue University.
Subject Area
Organic chemistry
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