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单齿磷配体混合物作为控制铑催化手性烯烃氢化反应中非对映选择性的一种手段。

Mixtures of monodentate P-ligands as a means to control the diastereoselectivity in Rh-catalyzed hydrogenation of chiral alkenes.

作者信息

Reetz Manfred T, Guo Hongchao

机构信息

Max-Planck-Institut für Kohlenforschung, Kaiser-Wilhelm-Platz 1, D-45470 Mülheim/Ruhr, Germany.

出版信息

Beilstein J Org Chem. 2005 Aug 26;1(1):3. doi: 10.1186/1860-5397-1-3.

DOI:10.1186/1860-5397-1-3
PMID:16542016
原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC1399451/
Abstract

The previously reported concept of using mixtures of monodentate ligands in a combinatorial manner in order to influence enantio- or regioselectivity of transition metal catalyzed processes has been extended to include diastereoselectivity. Accordingly, 1,2- and 1,3-asymmetric induction in the Rh-catalyzed hydrogenation of a chiral allylic alcohol and a chiral homo-allylic alcohol has been studied by using mixtures of monodentate P-ligands. It was found that appropriate 1:1 mixtures of two different P-ligands enhance the degree of diastereoselectivity relative to the use of the respective pure ligands themselves. Here, as in the previous cases regarding enantio- or regioselectivity, this type of combinatorial catalysis leads to improved catalytic profiles without the need to prepare new ligands.

摘要

先前报道的以组合方式使用单齿配体混合物来影响过渡金属催化过程的对映选择性或区域选择性这一概念已扩展至包括非对映选择性。相应地,通过使用单齿P-配体混合物,对手性烯丙醇和手性高烯丙醇的铑催化氢化反应中的1,2-和1,3-不对称诱导进行了研究。结果发现,相对于使用各自的纯配体,两种不同P-配体的适当1:1混合物可提高非对映选择性程度。在此,如同先前关于对映选择性或区域选择性的情况一样,这种组合催化方式无需制备新配体即可改善催化性能。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/25b0/1399451/cc08d75e5f67/Beilstein_J_Org_Chem-01-03-g005.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/25b0/1399451/b7643976af5d/Beilstein_J_Org_Chem-01-03-g002.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/25b0/1399451/1831892b621c/Beilstein_J_Org_Chem-01-03-g003.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/25b0/1399451/77260687cf2e/Beilstein_J_Org_Chem-01-03-g004.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/25b0/1399451/cc08d75e5f67/Beilstein_J_Org_Chem-01-03-g005.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/25b0/1399451/b7643976af5d/Beilstein_J_Org_Chem-01-03-g002.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/25b0/1399451/1831892b621c/Beilstein_J_Org_Chem-01-03-g003.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/25b0/1399451/77260687cf2e/Beilstein_J_Org_Chem-01-03-g004.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/25b0/1399451/cc08d75e5f67/Beilstein_J_Org_Chem-01-03-g005.jpg

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