Date of Award

1992

Publication Type

Doctoral Thesis

Degree Name

Ph.D.

Department

Chemistry and Biochemistry

Keywords

Chemistry, Organic.

Rights

info:eu-repo/semantics/openAccess

Abstract

Factors which influence the diastereoselectivity in the alkylation of the (R)-camphor imine of tert-butyl glycinate (24) were investigated in order to further refine the alkylation model. It was demonstrated that when alkylating 24 with various benzyl bromides or allyl bromide that the diastereoselectivity was dependent on the $\pi$-electron density of the alkylating agent, the metal cation of the enolate and the cosolvent used. Inferior selectivities (de's $$ 95%) were obtained when using HMPA as the cosolvent, Li or Na as the metal cation and alkylating agents with electron rich $\pi$-systems. Further study included the preparation of several camphor derivatives (ketopinic acid, methyl ketopinate, 3-hydroxycamphor, 1-hydroxymethyl camphor) which were utilized as chiral auxiliaries in the alkylation of their corresponding imines of tert-butyl glycinate. These investigations lead to the discovery of two new and unexpected reactions of the camphor skeleton. Finally, a new C$\sb2$ symmetric ketone, cis,anti,cis-tricyclo (6.3.0.0$\sp{3,7}\rbrack$undecan-2-one (91) was prepared in 91% ee. Initial efforts to use this ketone as a chiral auxiliary in the alkylation of chiral imines of tert-butyl glycinate failed since condensation of 91 with several amines was not possible. This lead to an investigation into the utility of cis,anti,cis-tricyclo (6.3.0.0$\sp{3,7}\rbrack$undecan-2-ol (92) as a chiral auxiliary. Source: Dissertation Abstracts International, Volume: 53-12, Section: B, page: 6300. Thesis (Ph.D.)--University of Windsor (Canada), 1992.

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