Development of Novel Catalytic Asymmetric Reactions

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1. A highly enantioselective arylation of olefins (asymmetric Heck reaction) was achieved by using aryl triflates as arylating reagents and a chiral palladium catalyst. (1) The reaction of 2, 3-dihydrofuran in the presence of 1, 8-bis (dimethylamino) naphthalene as a base gave 2-aryl-2, 3-dihydrofurans of 87-96% ee. (2) The reaction of N-substituted 2-pyrrolines gave 2-aryl-5-pyrrolines of up to 83% ee.2. Novel catalytic asymmetric reactions were developed by using a newly designed chiral monophosphine ligand (MOP). (1) Asymmetric hydrosilylation of 1-alkenes in the presence of a Pd-MOP catalyst gave optically active 2-silylalkanes, which were easily converted into 2-alkanols of 94-97% ee. (2) Catalytic asymmetric hydroboration of 1, 3-enynes gave optically active allenylboranes of up to 60% ee. (3) Optically active 3, 7-dimethylocta-1, 6-diene (70% ee) was prepared by reductive cleavage of geranyl acetate with formic acid in the presence of a Pd-MOP catalyst.3. A series of chiral ferrocenylbisphosphines containing an aminoalkyl side chain were prepared and their efficiency as a chiral ligand in the Au (I)- or Ag (I)-catalyzed asymmetric aldol reaction of isocyanoacetate was examined.4. Asymmetric double hydroboration of 1, 3-diene was performed with chiral phosphine-rhodium complexes.