Characterization of Two Stable Degradants of Palladium tBuXPhos Catalyst and a Unique Dearomatization Reaction

被引：19

作者：

Allgeier, Alan M. ^{[1
]}

Shaw, Bradley J. ^{[1
]}

Hwang, Tsang-Lin ^{[1
]}

Milne, Jacqueline E. ^{[1
]}

Tedrow, Jason S. ^{[1
]}

Wilde, Christopher N. ^{[1
]}

机构：

[1] Amgen Inc, Thousand Oaks, CA 91320 USA

来源：

ORGANOMETALLICS | 2012年 / 31卷 / 02期

关键词：

MIYAURA COUPLING REACTIONS; C-N; ARYL CHLORIDES; AMINATION REACTIONS; OXIDATIVE ADDITION; COMPLEXES; LIGANDS; PALLADACYCLES; PRECATALYSTS; ACTIVATION;

D O I：

10.1021/om200988f

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

Two stable degradants of palladium (t)BuXPhos catalyst have been synthesized from (t)BuXPhos and Pd-2(dba)(3)center dot CHCl3, isolated, and fully characterized. Complex 2 augments the known literature examples of palladacycles from this ligand family but is present as a rare four-membered-ring palladacycle, having activated the top ring of the ligand. Complex 3 is an unusual case of palladium-mediated dearomatization, whereby chloroform functionalizes the bottom ring, generating a palladium allyl complex. The mechanism is assigned to an electrophilic carbene attack where palladium directs attack of dichlorocarbene to the anti face of the bottom arene. The structures have been confirmed by NMR and single-crystal X-ray diffraction.

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页码：519 / 522

页数：4

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