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Transition Metal Catalysis in Water

水中的过渡金属催化

基本信息

批准号：
14078223
负责人：
UOZUMI Yasuhiro
金额：
$ 14.34万
依托单位：
Institute for Molecular Science (2004-2005)Okazaki National Research Institutes (2002-2003)
依托单位国家：
日本
项目类别：
Grant-in-Aid for Scientific Research on Priority Areas
财政年份：
2002
资助国家：
日本
起止时间：
2002 至 2005
项目状态：
已结题

来源：
https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-14078223/
关键词：
aquacatalysis transition metal organic synthesis stereoselectivity pincer complex 立体選択性

项目摘要

Organometallic pincer complexes containing terdentate monoanionic ligands composed of an anionic aryl carbon atom and two mutually trans-chelating donosites at the 2,6-positions of the aromatic ring have been attracting widespread interest in catalysis and material science. A wide range of NCN pincer palladium complexes, [4-tert-2,6-bis(N-alkylimino)phenyl]chloropalladium (alkyl = n-butyl, benzyl, cyclohexyl, t-butyl, adamantyl, phenyl, 4-methoxyphenyl), were readily prepared from trans-(4-tert-butyl-2, 6-diformyl-phenyl)chlorobis(triphenylphosphine)palladium via dehydrative introduction of the corre sponding alkylimino ligand groups (ligand introduction route) in excellent yields (71-98%). NMR studies on this route for forming pincer complexes revealed the intermediacy of [4-tert-2,6- bis(N-alkylimino)phenyl]chlorobis(triphenylphosphine)palladium which is in equilibrium with the corresponding NCN pincer complexes via coordination/dissociation of the intramolecular imino groups and triphenylphosphine ligands.Nitromethane was safely applied as a Cl nucleophile for palladium-catalyzed p-allylic substitution in water with amphiphilic PS-PEG resin-supported phosphine-palladium complexes. Catalytic asymmetric nitromethylation of cycloalkenyl esters was achieved in water as a single reaction medium under heterogeneous conditions using 5 mol % palladium of a PS-PEG resin-supported pallad ium-imidazoindolephosphine complex to give optically active (cycloalkenyl) nitromethanes with up to 98% ee. Water-based aerobic oxidation of alcohols and alfa-alkylation of methyl ketones with a variety of alcohols as alkylation reagents were also successfully achieved by using the amphiphilic resin-dispersion of nanometal (Pd, Pt) particle-catalysts.

由一个阴离子芳基碳原子和两个位于芳环2，6-位的相互反式螯合的单阴离子配体组成的金属夹状有机配合物在催化和材料科学领域引起了广泛的兴趣。[4-tert-2，6-bis(N-alkylimino)phenyl]chloropalladium(烷基=正丁基、苄基、环己基、叔丁基、金刚烷基、苯基、4-甲氧基苯基)是由反式-(4-叔丁基-2，6-diformyl-phenyl)chlorobis(triphenylphosphine)palladium)通过脱水引入相应的烷亚胺配体(配体引入路线)以极高的产率(71-98%)合成的。核磁共振研究表明，通过分子内亚氨基和三苯基膦配体的配位/解离，[4-Tert-2，6-bis(N-alkylimino)phenyl]chlorobis(triphenylphosphine)palladium]与相应的nCN钳形络合物处于平衡状态。硝基甲烷可以作为亲核试剂用于水中钯催化的对烯丙基取代反应。以水为单一反应介质，在非均相条件下，以聚乙二醇钯-咪唑并吲哚膦为催化剂，在水中实现了环烯基酯的不对称硝甲基化反应，得到光学活性的(环烯基)硝基甲烷。利用两亲性树脂分散的纳米金属(Pd，Pt)粒子催化剂，还成功地实现了醇的水基好氧氧化和甲基酮的α-烷基化反应。