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首页> 外文期刊>Organometallics >Stereocontrol in Preparation of Cyclopalladated Alkylaromatic Oximes and Evaluation of Their Stereoselective Esterase-Type Catalytic Activity
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Stereocontrol in Preparation of Cyclopalladated Alkylaromatic Oximes and Evaluation of Their Stereoselective Esterase-Type Catalytic Activity

机译：立体科技制备环戊基烷基芳族肟及其立体选择性酯酶型催化活性的评价

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摘要

The stereochemistry of 2'-methylbutyrophenone oxime, the rates of ortho-palladation of its E- and Z-isomers, and catalytic activity of the respective Pd complexes were studied. The full stereoisomeric composition of oximes was established for the first time by means of supercritical fluid chromatography on chiral polysaccharide column. It was shown that enantiomeric excesses of both E/Z-isomers of (S)-2'-methylbutyrophenone oxime (1S) and (R)-2'-methylbutyrophenone oxime (1R) were equal to 92 +/- 2. The cyclopalladation study revealed that while E-isomer is ortho-palladated very quickly its Z-counterpart does not enter this reaction. However, upon coordination to Pd(II), Z-oxime slowly isomerizes into E-form with fast subsequent cyclopalladation, so it was possible to perform ortho-palladation of E-oxime in kinetic resolution mode with removal of unreacted Z-oxime. Comparatively rare cis-structure of cyclopalladated oxime dimer was proved by means of single-crystal X-ray study. For the first time, it was shown that ortho-palladated chiral oximes behave as enantioselective catalyst in the hydrolysis of chiral esters.
机译：研究了2'-甲基丁基酮肟的立体化学，研究了其E-和Z-异构体的邻钯，以及各种Pd复合物的催化活性。通过手性多糖塔上的超临界流体色谱法首次建立肟的全立体异构体组合物。结果表明，（S）-2'-甲基丁基酮肟（1S）和（R）-2'-甲基丁基酮肟（1R）的E / Z-异构体的对映体过量等于92 +/- 2.环钯化研究表明，虽然E-异构体是邻滴磷酸盐，但其Z-anderpart不会进入该反应。然而，在与Pd（II）的协调时，Z-肟在快速随后的环铝化合物中缓慢地异构化成E形，因此可以在动力学分辨率模式下进行e-肟的正交渗透，从而除去未反应的Z-肟。通过单晶X射线研究证明了环戊烷化肟二聚体的相对罕见的顺式结构。首次表明，在手性酯的水解中表现出邻钯的手性肟表现在对映选择性催化剂中。

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