Chemoselective Oxidation of Polyols with Chiral Palladium Catalysts

被引：33

作者：

De Crisci, Antonio G. ^{[1
]}

Chung, Kevin ^{[1
]}

Oliver, Allen G. ^{[2
]}

Solis-Ibarra, Diego ^{[1
]}

Waymouth, Robert M. ^{[1
]}

机构：

[1] Stanford Univ, Dept Chem, Stanford, CA 94305 USA

[2] Univ Notre Dame, Dept Chem & Biochem, Mol Struct Facil, Notre Dame, IN 46556 USA

来源：

ORGANOMETALLICS | 2013年 / 32卷 / 07期

关键词：

AEROBIC ALCOHOL OXIDATION; MOLECULAR-ORBITAL METHODS; EFFECTIVE CORE POTENTIALS; SECONDARY ALCOHOLS; KINETIC RESOLUTION; BASIS-SETS; POLARIZATION FUNCTIONS; AIR OXIDATION; 3RD-ROW ATOMS; COMPLEXES;

D O I：

10.1021/om4001549

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

Chiral palladium-based catalysts derived from pyridinyl oxazoline (pyOx) ligands catalyze the oxidation of alcohols, including 1,2-diols, triols, and tetraols, with high regio- and chemoselectivity. Screening of various chiral oxazoline-derived ligands for the oxidation of a model diol, 1,2-propanediol (1,2-PD), revealed that the nature of the ligand had a significant influence on the activity and cliemoselectivity for oxidation of vicinal diols. The PyOx ligands containing an a-methyl substituent were the most active for the oxidation of 1,2-PD using benzoquinone as the terminal oxidant. Oxidation of vicinal diols and polyols occurs selectively at the secondary alcohol to afford a-hydroxy ketones in isolated yields of 62-87%. Chemoselective oxidation of meso-erythritol with the chiral [(S)-(alpha-Me(tert-Bu)PyOx)Pd(OAc)](2)[OTf](2) afforded (S)-erthyrulose in 62% yield and 24%

引用

页码：2257 / 2266

页数：10

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