Platinum-Catalyzed Substitution of Allylic Fluorides

被引：32

作者：

Benedetto, Elena ^{[1
]}

Keita, Massaba ^{[1
]}

Tredwell, Matthew ^{[1
]}

Hollingworth, Charlotte ^{[1
]}

Brown, John M. ^{[1
]}

Gouverneur, Veronique ^{[1
]}

机构：

[1] Univ Oxford, Chem Res Lab, Oxford OX1 3TA, England

来源：

ORGANOMETALLICS | 2012年 / 31卷 / 04期

基金：

英国工程与自然科学研究理事会;

关键词：

NUCLEOPHILIC-SUBSTITUTION; CARBON-ATOM; ENANTIOSELECTIVE FLUORINATION; (PI-ALLYL)PALLADIUM COMPLEXES; REDUCTIVE ELIMINATION; PALLADIUM; ALKYLATION; ALLYLATION; REACTIVITY; LIGAND;

D O I：

10.1021/om201029m

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

Ally! fluorides are reactive toward Pt-catalyzed alkylation with malonate and likewise toward N- and O-nucleophiles under mild conditions. The reactivity of fluoride as a leaving group equals or exceeds that of the esters and carbonates commonly employed in allylic alkylation. The order of leaving-group ability with Pt catalysts was found to be F >= OCO2Me >> OBz >= OAc. This discouraged the application of platinum catalysts for the reverse reaction, fluorination of allylic substrates. Fluoride displacement involves predominant or complete retention of configuration in all the observed cases, and this was confirmed as a general feature of Pt catalysis, the stereochemical integrity being as high or higher as in Pd catalysis for the examples chosen.

引用

页码：1408 / 1416

页数：9

共 69 条

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