Development of New Organic Reactions and Synthesis of Physiologically Active Substance

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Research objectives : the following six objectives have been studied. (1) development of new synthetic organic reactions and management of the research (R. Noyori), (2) development of new reactions based on the use of typical elements (H. Yamamoto), (3) synthesis of oligonucleotides (B. Hayakawa), (4) prostaglandin synthesis (M. Suzuki), (5) synthesis of anthracyclin antibiotics (K. Maruoka), (6) synthesis of alkaloids, terpines, and vitamines (M. Kitamura).Results : successful results are summarized as follows. (1) organozinc aided stereoselective conjugate addition to enones and selective momoalkylation of enolates ; selective propargylation of carbonyls ; catalysis of PG endoperoxides ; asymmetric reduction of carbonyls with BINAL-H ; TMSOTf catalyzed aldol-type reactions ; practical synthesis of BINAP ; BINAP-Rh catalyzed asymmetric hydrogenation of olefins ; BINAP-Ru (II) catalyzed asymmetric hydrogenation of functionalized olefins ; kinetic resolution of allylic alcohols by BINAP … More -Ru catalyzed hydrogenation ; asymmetric synthesis of diols by double stereodifferentiation ; kinetic resolution of a racemic hydroxy ketones ; assymmetric synthesis using dynamic kinetic resolution ; asymmetric 1, 3-hydrogen shift catalyzed by BINAP-Rh catalyst ; kinetic resolution of 4-hydroxy-2-cyclopentenone ; catalytic enantioselective alkylation using organozinc reagents and elucidation of the mechanism ; efficient Pd(O)-catalyzed deprotection of allyl- and allyloxycarbonyl protective groups in nucleosides and ncleotides ; synthesis of unsymmetrically (2'-5'), (3'-5') linked oligonucleotides. (2) amphiphilic alkylation using alliminium agents, MAD and MAT : synthesis of steroids, conjugate addition of enones, selective reduction of two different ketones ; organoaluminium-promoted Claisen rearrangement : synthesis of Lardolure and Recifeolide ; CAB catalysis in organic synthesis : asymmetric Diels-Alder reaction, Aldol reaction, enereaction ; stereoselective synthesis of geranyl- and neryl-metal reagents ; synthesis of Ubiquinone 10. (3) synthesis of extremely pure 60 mers of oligonucleotides ; direct synthesis of solid-anchored DNA oligomers. (4) extremely shot-step synthesis of prostaglandin E_2 ; general syntheis of PGs ; synthesis of isocarbacyclin, synthesis of punaglandins ; synthesis of a photoaffinity probe reagent for prostacyclin receptor. (5) asymmetric Hetero-Diels-Alder reaction based on the use of binaphthol modified chiral alunminium agent AL ; efficient in situ generation of chiral Lewis acid ; asymmetric ene and Claisen reactions with AL ; stereoselcctive C-glycosidation ; synthesis of pseudosugars ; efficient synthesis of a partial structure of FK506 ; efficient construction of anthracyclin skeletons. (6) BINAP-Ru catalyzed enantioselective hydrogenation of enamides ; synthesis of a key intermediate for general synthesis of isoquinoline alkaloids ; asymmetric hydrogenation of allylic alcohols ; BINAP-Ru catalyzed asymmetric hydrogenation of bifunctionalized ketones ; asymmetric synthesis of 1beta-methylcarbapenems ; asymmetric synthesis of beta-amino acids ; asymmetric synthesis of camitine, statine, and analogues ; stereoselective synthesis of threonine type compounds. Less