Part I. Solvolysis of Caryophyllen-8-Yl Derivatives: Model Reactions for Presilphiperfolanol Biogenesis. Part II. Stereochemistry of Lithium-Amine Reductions of Tetrasubstituted Epoxides and Phenylthiohydrins to Tertiary Alcohols
Shankar, Sriram
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https://hdl.handle.net/2142/84390
Description
Title
Part I. Solvolysis of Caryophyllen-8-Yl Derivatives: Model Reactions for Presilphiperfolanol Biogenesis. Part II. Stereochemistry of Lithium-Amine Reductions of Tetrasubstituted Epoxides and Phenylthiohydrins to Tertiary Alcohols
Author(s)
Shankar, Sriram
Issue Date
1997
Doctoral Committee Chair(s)
Coates, R.M.
Department of Study
Chemistry
Discipline
Chemistry
Degree Granting Institution
University of Illinois at Urbana-Champaign
Degree Name
Ph.D.
Degree Level
Dissertation
Keyword(s)
Chemistry, Organic
Language
eng
Abstract
A comparative study of the Li-amine reductions of model bicyclic tetrasubstituted epoxides and the corresponding trans-phenylthiohydrins was carried out to determine the stereochemistry and optimal reaction conditions for this transformation. Octalin, hydrindene, and bicyclo (3.3.0) octene epoxides were synthesized, and the product ratios from their reductions in NH$\sb3$ and EtNH$\sb2$ were determined and compared with those in ethylenediamine reported in the literature. Li-NH$\sb3$ reductions gave best selectivities. Li-EtNH$\sb2$ reductions were faster than Li-NH$\sb3$ reductions, and they showed selectivities comparable to those with Li-ethylenediamine reported. trans-1,2-Phenylthiohydrins of octalin, hydrindene, and bicyclo (3.3.0) octene were synthesized by ring opening of the corresponding epoxides with Et$\sb2$AlSPh. The reductions of the phenylthiohydrins and their respective phenylthioalkoxides were carried out in Li-NH$\sb3,$ and the product ratios were determined. The potential for regioselective ring opening of epoxides combined with the ease of reduction of phenylthiohydrins, and the selectivity of Li-amine reductions to give a thermodynamic distribution of alcohols makes this method very appealing.
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