2 Synthetic methods Part (iv) Heteroatom methods

Abstract

This chapter focuses on the organic chemistry of phosphorus, sulfur, selenium, tellurium, and silicon, particularly the formation of carbon–heteroatom bonds, and heteroatom facilitated carbon–carbon bond formation; the corresponding heterocyclic, free radical and transition metal chemistry is covered more thoroughly elsewhere. The review was compiled using a combination of on-line searching and selective reading of the literature.

Over the past few years Montchamp and co-workers have developed a useful set of synthetic protocols for the synthesis of phosphinates (Scheme 3) and are now working on asymmetric variants of some of these transformations, which will lead to products with a chiral centre at phosphorus (i.e. desymmetrisation of the two P–H bonds in substrates such as 13); some promising preliminary results towards this goal have already been achieved. Another highlight is exemplified by Scheme 30: silicon-based cross-coupling reactions have now passed the benchmark of being employed in total synthesis and will surely find further such employment both by the developers of this approach and other researchers.

A number of reviews of cross-coupling reactions appeared in 2002. “Thirty years of the cross-coupling reaction” were celebrated at a symposium in Kyoto, Japan in 2001, the proceedings of which form a special issue of the Journal of Organometallic Chemistry; individual papers therein and other reviews focusing on one particular heteroatom are noted in the corresponding section below. A more general review covers couplings of soft, non-organometallic nucleophiles with aryl halides (and pseudohalides).