cine Substitution and the Cu Effect in Stille Cross-Coupling Reactions: Mechanistic Perspectives and Synthetic Utility

cine Substitution arising from slow transmetallation occasionally occurs in classic Pd‐catalyzed Stille cross‐coupling reactions with sterically hindered vinyltin components. Mechanistic explanations of this “abnormal” cross‐coupling mode and the intriguing co‐catalytic effects of metallic Cu specie...

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Bibliographic Details
Published in:European Journal of Organic Chemistry 2010-12, Vol.2010 (35), p.6703-6718
Main Authors: Peng, Yu, Li, Wei-Dong Z.
Format: Article
Language:English
Subjects:
Chemistry
cine Substitution
Copper
Cross-cou­pling
Exact sciences and technology
Kinetics and mechanisms
Natural products
Organic chemistry
Reactivity and mechanisms
Stille reaction
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Summary:cine Substitution arising from slow transmetallation occasionally occurs in classic Pd‐catalyzed Stille cross‐coupling reactions with sterically hindered vinyltin components. Mechanistic explanations of this “abnormal” cross‐coupling mode and the intriguing co‐catalytic effects of metallic Cu species in restoring the ipso selectivity are summarized. Typical synthetic applications of this unique Cu effect and the advent of Cu‐catalyzed Stille‐type cross‐coupling are also demonstrated. cine Substitution resulting from slow transmetallation is an “abnormal” phenomenon in classic Stille cross‐couplings of sterically hindered vinyltins. Two mechanistic explanations are critically evaluated. As a method of countering cine substitution, co‐catalysis by CuI can accelerate transmetallation remarkably and on occasion restore the ipso selectivity.
ISSN:1434-193X
1099-0690
DOI:10.1002/ejoc.201000557