Müller Paul
Department of Organic Chemistry, University of Geneva, 30 Quai Ernest Ansermet, CH-1211 Geneva 4, Switzerland.
Acc Chem Res. 2004 Apr;37(4):243-51. doi: 10.1021/ar0202619.
Phenyliodonium ylides, readily available upon treatment of CH-acidic compounds such 1,3-dicarbonyl derivatives with iodobenzene diacetate, react in the presence of rhodium(II) or copper catalysts to afford products derived from carbenoid pathways. Chemo- and enantioselectivity of the reactions are identical to those of the corresponding diazocompounds, indicating metallocarbene intermediates with both precursors. An exception to this occurs in the intramolecular cyclopropanation of phenyliodonium ylides, where a competing uncatalyzed pathway intervenes at room temperature. When phenyliodonium ylides are generated in the presence of Rh(II) catalysts and olefins, they react in situ to afford cyclopropanes.
苯基碘叶立德可通过用二乙酸碘苯处理诸如1,3 - 二羰基衍生物等含CH酸性化合物轻松制得，在铑（II）或铜催化剂存在下反应，得到源自类卡宾途径的产物。这些反应的化学选择性和对映选择性与相应重氮化合物的相同，表明两种前体均生成金属卡宾中间体。但在苯基碘叶立德的分子内环丙烷化反应中存在例外情况，在室温下会有竞争的无催化途径介入。当在铑（II）催化剂和烯烃存在下生成苯基碘叶立德时，它们会原位反应生成环丙烷。
