| Co-Investigator(Kenkyū-buntansha) |
DOI Takayuki T.I.T., Chem.Eng., Assistant Professor, 工学部, 助手 (90212076)
MIYAZAWA Masahiro T.I.T., Chem.Eng., Assistant Professor, 工学部, 助手 (70209899)
YAMADA Haruo T.I.T., Chem.Eng., Assistant Professor, 工学部, 助手 (10175664)
TAKAHASHI Takashi T.I.T., Chem.Eng., Associate Professor, 工学部, 助教授 (80110724)
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| Research Abstract |
According to the proposed project, the Rh(I)-catalyzed hydroformylation, Pd(0)-catalyzed allylation reaction, and conjugate addition of various organozincates were carried out. Especially, the ligand effects on the chemo-, regio-, as well as stereoselectivity in these reactions were elucidated in terms of both steric and electronic origin. Thus, the report consists of the following items ;
1. Novel auxiliary ligands for rhodium(I) complexes and their selectivity in hydroformylation of alkenes-
With use of the chiral, chelating phsophorus ligands (L-L) having a wide bite angle (-120ﾟ), [RhH(CO)_2L-L] exhibited high catalytic activity in the hydroformylation of vinylarenes, but with low enantioselectivity.
2. Regio- and stereoselectivity in palladium(0)-catalyzed allylation-
Pd(0)-catalyzed allylation of 2,7-octadienyl acetate gave rise to a novel five-membered ring formation which crucially relied on acetic acid as a solvent. The novel cyclization via pi-allylpalladium intermediates with stereospecific 1,3-chirality transmission was realized in certain prostaglandin synthesis.
3. Conjugate addition of functionalized organozincates and their applications to organic syntheses-
Diastereoselective addition of particular(Z)-vinylzincates to 4-alkoxy-2-cyclopentenone, followed by an enolate trapping with propargylic iodide, completed the prostaglandin synthesis.
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