Computational Study on the C-Heteroatom Bond Formation via Stille Cross-Coupling Reaction: Differences between Organoheterostannanes Me3SnAsPh2 vs Me3SnPPh2

被引：11

作者：

Sosa Carrizo, E. Daiann ^{[1
]}

Fernandez, Israel ^{[2
]}

Martin, Sandra E. ^{[1
]}

机构：

[1] Univ Nacl Cordoba, CONICET, INFIQC, Fac Ciencias Quim,Dept Quim Organ, RA-5000 Cordoba, Argentina

[2] Univ Complutense Madrid, Dept Quim Organ 1, Fac Ciencias Quim, E-28040 Madrid, Spain

来源：

ORGANOMETALLICS | 2015年 / 34卷 / 01期

关键词：

DENSITY-FUNCTIONAL THEORY; OXIDATIVE ADDITION; ARYL HALIDES; ASSOCIATIVE TRANSMETALATION; PROMISING REAGENT; MECHANISM; PALLADIUM(0); DFT; COMPLEXES; CYCLIZATION;

D O I：

10.1021/om501027s

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

The formation of Cheteroatom bonds through the Stille cross-coupling reaction has been explored computationally within the density functional theory framework. To this end, the reaction profiles of the processes involving different aryl halides (PhCl, PhI) and heterostannanes (Me(3)SnZR(2), Z = As, P; R = Ph, Me) in the presence of palladium catalyst have been investigated and compared to gain more insight into the differential reactivity observed experimentally. In addition, the main features of the reaction steps where the heterostannanes are involved, namely, the transmetalation and reductive elimination reactions, have been analyzed in detail. It was found that the overall relative reaction profile for the transmetalation step involving heterostannanes with Z = P is energetically favored over that involving species having Z = As, which agrees with the experimental observations. This can be mainly ascribed to the relative strength of the SnZ bond, which is broken during the transmetalation step (Sn-P < Sn-As).

引用

页码：159 / 166

页数：8

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