Michael J. Rozema

The chemistry of polyfunctional organozinc and copper reagents

Recent developments of the chemistry of polyfunctional organozinc and copper reagents applied to organic synthesis are presented.

Preparation of polyfunctional diorganomercurials and their transmetallation to diorganozincs. Applications to the preparation of optically active secon

Abstract Two new methods of preparation of functionalized diorganomercurials have been developed. The first method involves a substitution reaction of (ICH 2 Their transmetallation with zinc dust (toluene, 80°C, 3–5 h) affords dialkylzincs which add enantioselectively to aldehydes in the presence of a ca

Selective multiple methylene insertion reactions mediated by iodomethylzine iodide: Mechanistic considerations and synthetic applications

Abstract The reaction of alkynylcoppers 1 with an excess of iodomethylzinc iodide selectively furnishes the quadruple methylene insertion copper organometallics 2 in fair to good yields. The mechanism of the reaction has been investigated and postulated intermediates such as 4 or 8 have been trapped with electrophiles like aldehydes or ketones in excellent yields. A new in situ preparation of propargylic copper derivatives 4 starting from readily available alkynylcopper compounds has been developed leading to homopropargylic alcohols in 80–95% yield.