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Rotation and inversion barriers in 2-lithio-2-phenyl-1,3-dithianes

Authors
Journal
Journal of Organometallic Chemistry
0022-328X
Publisher
Elsevier
Publication Date
Volume
156
Issue
1
Identifiers
DOI: 10.1016/s0022-328x(00)84882-2

Abstract

Abstract The barriers to phenyl rotation in 2-lithio-2-phenyl- cis-4,6-dimethyl-, 2-lithio-2-phenyl-4,4,6-trimethyl- and 2-lithio-2-phenyl- trans-4,6-dimethyl-1,3-dithiane are compared in tetrahydrofuran (THF) and hexamethylphosphortriamide (HMPA). In the first two cases, the barriers in THF are lower than those in HMPA, presumably because the lithio compound exists as a tight ion pair in THF but as a solvent-separated ion pair (with more delocalization of charge into the phenyl ring) in HMPA. However, in the trans-4,6-dimethyl compound the barriers are the same in the two solvents and nearly equal to the barriers for ring reversal. It is concluded that in this compound the rate-determining step for phenyl rotation may actually be ring reversal, at least in solvent HMPA.

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