Palladium-Catalyzed Synthesis of α-Trifluoromethyl Benzylic Amines via Fluoroarylation of gem-Difluoro-2-azadienes Enabled by Phosphine-Catalyzed Formation of an Azaallyl-Silver Intermediate

被引：50

作者：

Daniel, Paige E. ^{[1
]}

Onyeagusi, Chibueze I. ^{[1
]}

Ribeiro, Anthony A. ^{[2
,3
]}

Li, Kangnan ^{[1
]}

Malcolmson, Steven J. ^{[1
]}

机构：

[1] Duke Univ, Dept Chem, Durham, NC 27708 USA

[2] Duke Univ, NMR Ctr, Durham, NC 27710 USA

[3] Duke Univ, Dept Radiol, Durham, NC 27710 USA

来源：

ACS CATALYSIS | 2019年 / 9卷 / 01期

关键词：

palladium; silver; fluorine; phosphene; azadiene; cross-coupling; REGIOSELECTIVE ARYLATION; ASYMMETRIC-SYNTHESIS; UMPOLUNG REACTIONS; IMINES; DERIVATIVES;

D O I：

10.1021/acscatal.8b03999

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：

We report the synthesis of alpha-trifluoromethyl benzylic amines through the vicinal fluoroarylation of gem-difluoro-2-azadienes. Our studies indicate that XPhos plays an important role as a phase transfer catalyst that promotes the addition of AgF to the difluoroazadiene, generating an alpha-trifluoromethyl azaallyl-silver intermediate that we have characterized by NMR spectroscopy. This intermediate likely transmetallates to Pd, coupling several aryl iodides to deliver products in up to 90% yield. Modification of the azadiene's activating group facilitates challenging cross-couplings.

引用

页码：205 / 210

页数：11

共 36 条

[1]

Blackburn C., 2014, U.S. Pat. Appl. US, Patent No. [20140275093A1, 20140275093]

[2] Intramolecular dipolar cycloaddition reactions of azomethine ylides [J].