Lihua Yao

Defense Date

2-23-2011

Graduation Date

Spring 2011

Availability

Immediate Access

Submission Type

thesis

Degree Name

MS

Department

Chemistry and Biochemistry

Committee Chair

Fraser Fleming

Committee Member

Bruce Beaver

Committee Member

Paul Johnson

Keywords

Transmissive olefination, [3, 3] Rearrangement, Alkenenitriles, Grignard reagents, Allylic or allenic halides, Niobium halides

Abstract

Part 1. Grignard reagents readily add to alkenenitriles bearing an adjacent hydroxyl group to afford Z-alkenenitriles with transmissive relocation of the C=C bond. Mechanistically the transmissive olefination is consistent with rearrangement through a cyclic 6-membered transition structure in which the formal displacement of hydroxide occurs by forming magnesium oxide.

Part 2. Addition of niobium halides to a series of allylic or propargylic alkoxides directly provides allylic or allenic halides. Halogenation formally occurs through a metalla-halo-[3, 3] rearrangement although at least these different mechanisms may operate competitively. Transposition of the olefin is equally effective for allylic alkoxides prepared by necleophilic addition, deprotonation, or reduction.

Format

PDF

Language

English

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