Electron Transfer Phenomena between Hetero Atoms and Their Characteristics and Applications

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Electron transfer between different elements has been intensively investigated from mechanistic and synthetic view points. The present cooperative research covers (1) electron transfer in two and three component metal redox systems, (2) electron transfer between organometalic complexes and organic compounds, (3) photo- and electrochemically induced electron transfer reactions, and (4) their synthetic applications. In the first category, newly designed two and three components metal redox systems, e.g., Ti/Zn, Ni/Zn, Nb/Zn, Ta/Zn, Pb/Al, Ti/Al, and Ni/Pb/Al may provide potential electron transfer systems, each of which can promote the characteristic carbon-carbon bond making reactions. The electron transfer systems comprising transition metal complexes and organic compounds have opened unique entries to various highly selective functionalization of olefins and silyl compounds. Electron transfer reaction between enzyme complexes in biological system has been also investigated using porphyrin dimmer linked by polymethylene diamide bond as a model system. On the other hand, under the plioto- and electrochemical conditions, the combinations of metal and organic redoxes, e.g., heteroaromatic o-quinones/NADH, copper complex/allyl halides, phenanthrene/group 4B metal complexes, and copper(II) salts/vinyl bromides, have been found to work as an efficient electron transfer system. The above mentioned electron transfer reactions can be applied successfully to various synthetic purposes, particularly, to enantio- and diastereoselective carbon-carbon bond formation, e.g., asymmetric [2+2]cycloaddition, asymmetric glyoxylate-ene reaction, oxygenation and hydrosilylation of olefins, cyclization of eneynes and diynes, rotamer distribution controlled C=C face differentiation, chirafity transfer of L-valine to homoallylamines and others.