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首页> 外文期刊>Dalton transactions: An international journal of inorganic chemistry >Tuning ligand structure in chiral bis(phosphite) and mixed phosphite-phosphinite PCP-palladium pincer complexes
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Tuning ligand structure in chiral bis(phosphite) and mixed phosphite-phosphinite PCP-palladium pincer complexes

机译：调整手性双（亚磷酸酯）和亚磷酸酯-次亚膦酸酯PCP-钯夹杂配合物的配体结构

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摘要

A range of chiral resorcinol bis(phosphite) and phosphite-phosphinite ligands were produced and their propensity to form palladium PCP-pincer complexes examined. The ease of base-assisted C-H palladation of the ligands falls in the order bis(phosphinite) > phosphite-phosphinite > bis(phosphite). The catalytic activity of the complexes in the asymmetric allylation of benzaldehyde with allyl tributyltin was examined and it was found that, contrary to expectations, ligands with 3,3'-disubstituted BINOL residues show poorer activity and stereoselectivity than unsubstituted BINOL analogues. In addition the order of activity of the pincer complexes was established as bis(phosphite) > phosphite-phosphinite > bis(phosphinite). Crystal structures of representative examples of a 3,3'-disubstituted BINOL, mono- and bis(phosphite) ligands based on 2,4-di-tert-butyl resorcinol and Pd complexes of two of the chiral complexes are presented.
机译：制备了一系列手性间苯二酚双（亚磷酸酯）和亚磷酸酯-次亚膦酸酯配体，并研究了它们形成钯PCP-钳子复合物的倾向。配体的碱辅助C-H轻触化容易程度依次为双（亚膦酸酯）>亚磷酸酯-亚膦酸酯>双（亚磷酸酯）。研究了该络合物在苯甲醛与烯丙基三丁基锡的不对称烯丙基化反应中的催化活性，发现与预期相反，具有3,3'-二取代BINOL残基的配体比未取代的BINOL类似物具有更差的活性和立体选择性。另外，钳夹配合物的活性顺序被确定为双（亚磷酸酯）>亚磷酸酯-亚膦酸酯>双（亚膦酸酯）。给出了3，3′-二取代的BINOL，基于2，4-二叔丁基间苯二酚和两个手性配合物的Pd配合物的单和双（亚磷酸酯）配体的代表性实例的晶体结构。

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