Generation and utilization of copper(I) ate complexes from diastereomeric and enantiomeric alkylmercury reagents Academic Article uri icon

abstract

  • Treatment of alkylmercuric halides in succession with 1 equiv of iodo(tri-n-butylphosphine)copper(I) and 3 equiv of tert-butyllithium at −78° in tetrahydrofuran results in formation of a reactive ate complex which incorporates the alkyl group originally bonded to mercury. The reactions of this alkyl group resemble those of a lithium dialkylcuprate: it can be alkylated with alkyl halides and coupled with a tert-butyl moiety by oxidation with nitrobenzene; it does not, however, undergo conjugate additions to α,β-unsaturated ketones. In certain instances, but not always, the overall conversion from alkylmercuric halide to product takes place with retention of configuration at the carbon originally bonded to mercury. The structure(s) of these ate complexes cannot be established from the available data, but qualitative evidence suggests that lithium, copper(I), and mercury(II) are all present in the metal core. Possible applications and limitations of these complexes in synthesis are briefly outlined. © 1974, American Chemical Society. All rights reserved.

author list (cited authors)

  • Bergbreiter, D. E., & Whitesides, G. M

complete list of authors

  • Bergbreiter, David E||Whitesides, George M

publication date

  • January 1, 1974 11:11 AM