C(sp3)-F reductive elimination from alkylgold(III) fluoride complexes

被引：125
作者：
Mankad, Neal P. [1 ]
Toste, F. Dean [1 ]
机构：
[1] Univ Calif Berkeley, Dept Chem, Berkeley, CA 94720 USA
来源：
CHEMICAL SCIENCE | 2012年 / 3卷 / 01期
基金：
美国国家科学基金会;
关键词：
C-C; CARBON-CARBON; FLUORINATION; BONDS; GOLD; CATALYSIS; REACTIVITY; PALLADIUM; MECHANISM; ISOMERIZATION;
D O I：
10.1039/c1sc00515d
中图分类号：
O6 [化学];
学科分类号：
0703 ;
摘要：
Rare examples of C(sp(3))-F reductive elimination were observed from several cis-F2Au(R)(IPr) intermediates generated by oxidation of (IPr)AuR complexes with XeF2. For R groups bearing beta-hydrogens, beta-hydride elimination was competitive with C(sp(3))-F reductive elimination. For strained cyclic R groups and most acyclic R groups lacking b-hydrogens, carbocation-like rearrangements occurred prior to C(sp(3))-F reductive elimination. Kinetics of the decay of one cis-F2Au(R)(IPr) species, stereochemical analysis of reductive elimination with a chiral R group, and DFT analysis collectively suggest C(sp(3))-F reductive elimination proceeding through transient cationic [(IPr)Au(F)(R)](+) intermediates with significant ionization of the Au-alkyl bonds.
引用
收藏
页码：72 / 76
页数：5
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