Rhodium-Catalyzed Asymmetric Dehydrocoupling: Enantioselective Synthesis of a P-Stereogenic Diphospholane with Mistake-Correcting Diastereoselectivity

被引：2

作者：

Chachula, Sarah T. ^{[1
]}

Scheetz, Perry M. ^{[1
]}

Zureick, Andrew H. ^{[1
]}

Hughes, Russell P. ^{[1
]}

Glueck, David S. ^{[1
]}

Hernandez, Ritchie E. ^{[2
]}

Figueroa, Joshua S. ^{[2
]}

Rheingold, Arnold L. ^{[2
]}

机构：

[1] Dartmouth Coll, Dept Chem, Burke Lab 6128, Hanover, NH 03755 USA

[2] Univ Calif San Diego, Dept Chem, 9500 Gilman Dr, La Jolla, CA 92093 USA

来源：

ORGANOMETALLICS | 2023年 / 42卷 / 13期

基金：

美国国家科学基金会;

关键词：

IHR REAKTIVES VERHALTEN; STEREOCHEMICAL LABILITY; PYRAMIDAL INVERSION; PHOSPHINES; DIPHOSPHINES; REACTIVITY; LIGANDS; ACTIVATION; COMPLEXES; SUBSTRATE;

D O I：

10.1021/acs.organomet.3c00188

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

Catalytic asymmetric dehydrocoupling of secondary phosphines is a potentially valuable route to enantiomerically enriched P-stereogenic diphosphines for use as ligands or building blocks for chiral bis(phosphines). Rh(diphos*) catalyst precursors converted a rac/ meso mixture of PhP(CH2)(3)PPh(1) to the C-2-symmetric Pstereogenic anti-diphospholane PhP(CH2)(3)PPh (2) in up to a 58:42 enantiomeric ratio (er) with complete diastereoselectivity via catalyst mediated isomerization of the intermediate syn-diphospholane 3 to 2 (mistake correction by conversion of the diastereomer meso-3 to chiral C-2-2). NMR studies of catalytic reactions identified the resting state Rh((R,R)-i-Pr-DuPhos) PhP(CH2)(3)PPh (4) and suggested a proposed mechanism for stereocontrolled P-P bond formation via oxidative addition and reductive elimination steps.

引用

页码：1448 / 1453

页数：6

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