Asymmetric Nucleophilic Catalysis with an Octahedral Chiral-at-Metal Iridium(III) Complex

被引：42

作者：

Cruchter, Thomas ^{[1
]}

Medvedev, Michael G. ^{[2
,3
]}

Shen, Xiaodong ^{[1
]}

Mietke, Thomas ^{[1
]}

Harms, Klaus ^{[1
]}

Marsch, Michael ^{[1
]}

Meggers, Eric ^{[1
]}

机构：

[1] Philipps Univ Marburg, Fachbereich Chem, Hans Meerwein Str 4, D-35043 Marburg, Germany

[2] AN Nesmeyanov Inst Organoelement Cpds RAS, Xray Struct Lab, Vavilova St 28, Moscow 119991, Russia

[3] ND Zelinsky Inst Organ Chem RAS, Leninsky Prospect 47, Moscow 119991, Russia

来源：

ACS CATALYSIS | 2017年 / 7卷 / 08期

基金：

俄罗斯科学基金会;

关键词：

nucleophilic catalyst; Lewis base catalysis; asymmetric catalysis; iridium; chiral-at-metal; acyl transfer; ENANTIOSELECTIVE ACYL TRANSFER; NONENZYMATIC KINETIC RESOLUTION; COMPACT EFFECTIVE POTENTIALS; BOND DONOR CATALYSTS; EXPONENT BASIS-SETS; STEGLICH REARRANGEMENT; SECONDARY ALCOHOLS; BETA-LACTAMS; PROPARGYLIC ALCOHOLS; OXAZOL-5-ONE ANIONS;

D O I：

10.1021/acscatal.7b01296

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：

Herein, we report about the design, synthesis, and application of a nucleophilic octahedral chiral-only-at metal iridium(III) complex. We demonstrate that the enantiopure form of this complex serves as an efficient catalyst for the asymmetric Steglich rearrangement of O-acylated azlactones (up to 96% ee and 99% yield) and the related asymmetric Black rearrangement of O-acylated benzofuranones (up to 94% ee and 99% yield). We provide insight into the mechanisms of these two acyl migration reactions and the catalyst's manner of chiral recognition with crystal structures of the active catalyst and a catalysis intermediate analog, as well as with quantum chemical calculations based on them. Furthermore, we demonstrate that the presented catalyst also efficiently catalyzes the asymmetric reaction between aryl alkyl ketenes and 2-cyanopyrrole to give the corresponding alpha-chiral N-acyl pyrroles (up to 95% ee and 99% yield).

引用

页码：5151 / 5162

页数：12