Development of Novel Chiral Synthon by Using Cationic Palladium Complexes

1998 Fiscal Year Final Research Report Summary

• Project/Area Number: 09650954
• Research Category: Grant-in-Aid for Scientific Research (C)
• Allocation Type: Single-year Grants
• Section: 一般
• Research Field: Synthetic chemistry
• Research Institution: Nagoya University
• Principal Investigator: MURATA Shizuaki Graduate Scholl of Human Informatics, Nagoya University Associate Professor, 大学院・人間情報学研究科, 助教授 (50157781)
• Project Period (FY): 1997 – 1998
• Keywords: palladium complex / catalyst / phosphine ligand / alkanesulfinic acid / polycyclopentadiene / 31P NMR / hydroslufination / hydrosilasulfination

Research Abstract

Reactions of palladium triflate with 2 equiv. of didentate phosphine ligands, R_2P(CH_2)_nPR_2 (n=1,2,3), afforded cationic palladium triflate complexes, L_2Pd^<2+>(OTf)_2, in high yields. Reactions with 4 equiv. of monodentate phosphines, R_3P, gave cationic palladium complexes with acetonitrile, (R_3P)_<4-n> (CH_3CN)_nPd^<2+>(OTf)_2. Depending on the structure of phosphines, structures of these complexes with acetonitrile were different. For example, the tetrakis(tributyl)phosphine complex was obtained in the case of tri(n-butyl)phosphine, and tris(triphenyl) or tris(tri t-butyl)phosphine comples were obtained in the case of Ph_3P or (t-Bu)_3P.The complexes with 2 phosphines were obtained from reactions with (i-Pr)_3P and (c-Hex)_3P.It is found by ^<31>P NMR studies on the obtained complexes that those complexes existed as dynamic equiriblium mixture in acetonitrile solutions. The results were reported in 45^<th> symposium for organometallic chemistry (1998, Tokyo).
Catalytic natures of the complexes with didentate phosphine ligands toward hydroslufination and polymerization of cyclopentadiene were found. Application to hydrosilasulfination was under investigation. A chiral alkanesulfinic acid was prepared from optically active camphorsulfonic acid.