Atroposelective Transfer Hydrogenation of Biaryl Aminals via Dynamic Kinetic Resolution. Synthesis of Axially Chiral Diamines

被引：39

作者：

Carmona, Jose A. ^{[1
,2
]}

Rodriguez-Franco, Carlos ^{[1
,2
]}

Lopez-Serrano, Joaquin ^{[1
,2
,3
]}

Ros, Abel ^{[1
,2
]}

Iglesias-Siguenza, Javier ^{[4
,5
]}

Fernandez, Rosario ^{[4
,5
]}

Lassaletta, Jose M. ^{[1
,2
]}

Hornillos, Valentin ^{[1
,4
,5
]}

机构：

[1] Inst Invest Quim CSIC US, Seville 41092, Spain

[2] Ctr Innovac Quim Avanzada ORFEO CINQA, Seville 41092, Spain

[3] Univ Seville, Dept Quim Inorgan, Seville 41092, Spain

[4] Univ Seville, Dept Quim Organ, Seville 41012, Spain

[5] Ctr Innovac Quim Avanzada ORFEO CINQA, Seville 41012, Spain

来源：

ACS CATALYSIS | 2021年 / 11卷 / 07期

关键词：

asymmetric catalysis; dynamic kinetic resolution; transfer hydrogenation; axial chirality; diamines; ASYMMETRIC TRANSFER HYDROGENATION; ATROPO-ENANTIOSELECTIVE SYNTHESIS; BRONSTED ACID; NATURAL-PRODUCTS; LIGANDS; BINOL; DESYMMETRIZATION; ATROPISOMERISM; ACTIVATION; CATALYSIS;

D O I：

10.1021/acscatal.1c00571

中图分类号：

O64 [物理化学（理论化学）、化学物理学];

学科分类号：

070304 ; 081704 ;

摘要：

An efficient dynamic kinetic resolution (DKR) approach for the synthesis of axially chiral diamines has been developed on the basis of a ruthenium-catalyzed enantioselective transfer hydrogenation. The strategy relies on the configurational instability of cyclic biaryl aminal precursors in equilibrium with their amino-imine open forms, as supported by DFT calculations. This protocol features a broad substrate scope of aliphatic amines and biaryl scaffolds and proceeds under very mild conditions, allowing the preparation of BINAM homologues in good to high yields and nearly perfect enantioselectivities (up to 99% ee).

引用

页码：4117 / 4124

页数：8

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