|Budget Amount *help
¥13,000,000 (Direct Cost: ¥13,000,000)
Fiscal Year 2003: ¥1,800,000 (Direct Cost: ¥1,800,000)
Fiscal Year 2002: ¥3,500,000 (Direct Cost: ¥3,500,000)
Fiscal Year 2001: ¥7,700,000 (Direct Cost: ¥7,700,000)
This project focuses the development of carbon-carbon bond formation on the basis of multi-component coupling catalyzed by group 9 metal complex in one-pot procedure. Along the proposed strategy on rhodium-catalyzed reactions we successfully obtained the following results ; (1) the formation of bicyclo[3.3.0]octenone frameworks by the one-pot reactions among a hydrosilane, a 1,6-diyne, and CO and its application to the synthesis of hirsutene, (2) exploitation of a new method for the construction of 4,5, and 6-membered lactones by the incorporation of CO into alkynylalcohols and transformation of spiro-type γ-lactones to bicyclic ketones, (3) exploitation of a new method for the construction of 4,5,6, and 7-membered lactams by the incorporation of CO into alkynylamines, and (4) annulative long range silylformylation of hept-1-ene-6-ynes. We also realized a new three-component coupling under neutral conditions as follows ; formal hydrocarbamoylation and hydroallylation toward electron-deficient alkenes and a new Mannich type coupling triggered by the oxydative addition of a hydrosilane to low-valent rhodium metal. It was also revealed that an Ir-cationic complex shows strong Lewis acidity in CH_2Cl_2 and behaves as an efficient catalyst for aldol coupling, Michael type coupling, direct substitution of allylic alcohols and selective substitution of propargylic esters in reactions involving enoxy silane as a nucleophile.