Stille Coupling of Alkynyl Stannane and Aryl Iodide, a Many-Pathways Reaction: The Importance of Isomerization

Autor:	Mónica H. Pérez-Temprano, Juan A. Casares, Ana M. Gallego, Pablo Espinet
Rok vydání:	2011
Předmět:	Aryl Organic Chemistry chemistry.chemical_element Photochemistry Stannane Oxidative addition Medicinal chemistry Catalysis Stille reaction Inorganic Chemistry chemistry.chemical_compound Transmetalation chemistry Physical and Theoretical Chemistry Isomerization Palladium
Zdroj:	Organometallics. 30:611-617
ISSN:	1520-6041 0276-7333
DOI:	10.1021/om100978w
Popis:	The kinetics of the Stille reaction between C6Cl2F3I and PhCCSnBu3 have been studied for the whole catalytic system and for transmetalations as separate steps. The use of (trifluorodichlorophenyl)palladium derivatives slows down the reactions and allows for the observation of the intermediates cis- and trans-[Pd(C6Cl2F3)I(PPh3)2]. The first is formed in the oxidative addition step and isomerizes to the second. Both were studied as catalysts for the whole cycle. The kinetic study compares the relevance of the transmetalation step on each isomer. The competing transmetalations produce both cis- and trans-[Pd(C6Cl2F3)(PhCC)(PPh3)2]. The former undergoes very fast C−C coupling, while the second accumulates in solution due to extremely slow isomerization. Thus, the system is a case study of the effect of competing pathways in the Stille reaction and its consequences on the performance of the catalytic process.
Databáze:	OpenAIRE
Externí odkaz:	https://explore.openaire.eu/search/publication?articleId=doi_________::b11d0d7e5ffb951e3e8a699d75e6da4d https://doi.org/10.1021/om100978w Zobrazit plný text záznamu