Selectivity Switch in the Synthesis of Vinylgold(I) Intermediates

被引：109

作者：

Hashmi, A. Stephen K. ^{[1
]}

Schuster, Andreas M. ^{[1
]}

Gaillard, Sylvain ^{[2
,3
]}

Cavallo, Luigi ^{[4
,5
,6
]}

Poater, Albert ^{[7
]}

Nolan, Steven P. ^{[2
]}

机构：

[1] Heidelberg Univ, Inst Organ Chem, D-69120 Heidelberg, Germany

[2] Univ St Andrews, EaStCHEM Sch Chem, St Andrews KY16 9ST, Fife, Scotland

[3] Univ Caen, ENSICAEN, Lab Chim Mol & Thioorgan, INC3M,UMR 6507,FR 3038, F-14050 Caen, France

[4] Univ Salerno, Dipartimento Chim, I-84084 Fisciano, Italy

[5] King Abdullah Univ Sci & Technol, KAUST Catalysis Ctr, Thuwal 239556900, Saudi Arabia

[6] King Abdullah Univ Sci & Technol, Div Chem & Life Sci & Engn 4700, Thuwal 239556900, Saudi Arabia

[7] Univ Girona, Catalan Inst Water Res ICRA, E-17003 Girona, Spain

来源：

ORGANOMETALLICS | 2011年 / 30卷 / 22期

基金：

英国工程与自然科学研究理事会;

关键词：

HOMOGENEOUS GOLD CATALYSIS; N-HETEROCYCLIC CARBENE; C-H BONDS; STRUCTURAL-CHARACTERIZATION; PLATINUM CATALYSIS; SOLUTION BEHAVIOR; COMPLEXES; ALKYNES; HYDROAMINATION; ALLENES;

D O I：

10.1021/om2009556

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

An unexpected regioselectivity reversal was observed in the synthesis of vinylgold(I) complexes from propargyl carboxamides. The use of [Au(IPr)(OH)] affords preferentially vinylgold(I) complexes resulting from a 5-exo-dig cyclization, whereas the use [Au(IPr)](+) species, generated in situ starting from [Au(IPr)(Cl)] and AgOTf, leads to vinylgold(I) complexes which form via a 6-endo-dig cyclization, This unexpected "selectivity switch" for this cyclization led us to propose two different reaction pathways enabling the formation of the two different products. One mechanism involves the [Au(IPr)](+) species with "classical" pi activation of the alkyne framework of the carboxamides, and the second represents an "unusual" use of the basic Bronsted character of [Au(IPr)(OH)). Mechanistic and DFT studies support the mechanistic hypotheses.

引用

页码：6328 / 6337

页数：10

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