有機金属活性種の開発とその合成化学的展開

Abstract

The reactivity features of photochemically and chemically generated reactive species from organometallic compounds and their applications in organic synthesis are described. The reactive species include exciplexes, radical ions, and radicals involving group 14 organometallic compounds, and also iron complexes generated from Fe3 (CO) 12 and Bu4NFe(CO)3NO. By utilizing the specific chemical properties of these reactive species, a variety of new, highly selective synthetic reactions have been developed. The typical examples of the developed reactions are as follows : 1) synthesis of Si-and Ge-containing spiro and cyclophane compounds, 2) photo-allyl and arylmethylation of aromatic nitriles, 3) photo-allylation and silylation of electron-deficient alkenes, 4) double vicinal C-C bond formation on electron-deficient alkenes, 5) cyclodimerization of α, β-unsaturated carbonyl compounds, 6) pyrrole formation via reductive deoxygenation of dihydro-1, 2-oxazines, 7) regioselective nucleophilic and electrophilic addition to the allylic ligands of (η3-allylic) Fe (CO)2NO complexes, and 8) 1, 4-functionalization of 1, 3-dienes. The methods for enhancing the efficiencies and selectivities of photoreactions involving electron-transfer are also described.