Enantioselective Pd(II)-Catalyzed Aerobic Oxidative Amidation of Alkenes and Insights into the Role of Electronic Asymmetry in Pyridine-Oxazoline Ligands

被引：106

作者：

McDonald, Richard I. ^{[1
]}

White, Paul B. ^{[1
]}

Weinstein, Adam B. ^{[1
]}

Tam, Chun Pong ^{[1
]}

Stahl, Shannon S. ^{[1
]}

机构：

[1] Univ Wisconsin, Dept Chem, Madison, WI 53706 USA

来源：

ORGANIC LETTERS | 2011年 / 13卷 / 11期

关键词：

WACKER-TYPE CYCLIZATION; MOLECULAR-OXYGEN; INTRAMOLECULAR AMINOPALLADATION; BOND FORMATION; C-N; COMPLEXES; CATALYSIS; CARBON; CYCLIZATION/HYDROSILYLATION; HETEROCYCLES;

D O I：

10.1021/ol200784y

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

Enantioselective intramolecular oxidative amidation of alkenes has been achieved using a (pyrox)Pd(II)(TFA)(2) catalyst (pyrox = pyridine-oxazoline, TFA = trifluoroacetate) and 02 as the sole stoichiometric oxidant. The reactions proceed at room temperature in good-to-excellent yields (58-98%) and with high enantioselectivity (ee = 92-98%). Catalyst-controlled stereoselective cyclization reactions are demonstrated for a number of chiral substrates. DFT calculations suggest that the electronic asymmetry of the pyrox ligand synergizes with steric asymmetry to control the stereochemical outcome of the key amidopalladation step.

引用

页码：2830 / 2833

页数：4

共 43 条

[1] A new asymmetric Wacker-type cyclization and tandem cyclization promoted by Pd(II)-spiro bis(isoxazoline) catalyst [J].