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高效钯催化的酮和醛的不对称烯丙基烷基化反应。

Efficient palladium-catalyzed asymmetric allylic alkylation of ketones and aldehydes.

机构信息

School of Chemistry and Chemical Engineering, Shanghai Jiao Tong University, 800 Dongchuan Road, Shanghai 200240, PR China.

出版信息

Org Biomol Chem. 2011 Mar 21;9(6):1871-5. doi: 10.1039/c0ob00915f. Epub 2011 Jan 31.

Abstract

Palladium-catalyzed asymmetric allylic alkylation of ketones, via enamines generated in situ as nucleophiles, were carried out smoothly with chiral metallocene-based P,N-ligands. Under the same conditions, however, reactions of aldehydes could hardly be observed. Subsequently, this obstacle was resolved by using chiral metallocene-based P,P-ligands. Both ketones and aldehydes afforded excellent enantioselectivities with up to 98% ee and 94% ee, respectively.

摘要

手性茂金属 P,N-配体催化酮的烯丙基不对称烷基化反应,通过原位生成的烯胺作为亲核试剂,反应可以顺利进行。然而,在相同条件下,醛的反应几乎观察不到。随后,通过使用手性茂金属 P,P-配体解决了这一障碍。酮和醛都以高达 98%的对映选择性和 94%的对映选择性得到了极好的结果。

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