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Development of Novel Chiral Synthon by Using Cationic Palladium Complexes

Development of Novel Chiral Synthon by Using Cationic Palladium Complexes
利用阳离子钯配合物开发新型手性合成子
批准号:
09650954
负责人:
MURATA Shizuaki
金额:
$1.92万
依托单位:
依托单位国家:
日本
项目类别:
Grant-in-Aid for Scientific Research (C)
财政年份:
1997
资助国家:
日本
项目状态:
已结题
起止时间:
1997 至 1998

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中文摘要
翻译
三氟甲磺酸钯与2当量的三氟甲磺酸钯的反应。以二齿膦配体R_2P(CH_2)_nPR_2(n= 1,2,3)为配体,合成了阳离子三氟甲磺酸钯配合物L_2Pd^<2+>(OTf)_2。与4当量的反应用单齿膦配体R_3P与乙腈反应,得到阳离子钯配合物(R_3P)_(<4-n>CH_3CN)_nPd^(OTf)_2。根据膦的结构不同,这些配合物与乙腈的结构不同。例如,三正丁基膦可得到四丁基膦配合物,三三苯基膦或三叔丁基膦可得到三丁基膦配合物,(i-Pr)_3P和(c-Hex)_3P可得到两个膦配合物,它们在<31>乙腈溶液中以动态平衡混合物的形式存在。研究结果已在第45届<th>有机金属化学学术会议(1998年,东京)上发表,发现了双齿膦配体配合物对环戊二烯加氢磺化和聚合的催化作用,并正在探索其在硅氢化磺化反应中的应用。以光学活性的邻苯二磺酸为原料,合成了一种手性亚磺酸。
英文摘要
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.
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