The Role of Fluorine Substituents in the Regioselectivity of Intramolecular C–H Bond Functionalization of Benzylamines at Palladium(II)

Autor:	Ian J. S. Fairlamb, Jessica Milani, Natalie E. Pridmore, Adrian C. Whitwood, Robin N. Perutz
Rok vydání:	2015
Předmět:	C h bond Chemistry Stereochemistry Organic Chemistry Regioselectivity chemistry.chemical_element Crystal structure Ring (chemistry) Medicinal chemistry Inorganic Chemistry Intramolecular force Fluorine Surface modification Physical and Theoretical Chemistry Palladium
Zdroj:	Organometallics. 34:4376-4386
ISSN:	1520-6041 0276-7333
DOI:	10.1021/acs.organomet.5b00608
Popis:	The effect of fluorine substituents on the regioselectivity of intramolecular reactions of mono- and difluorinated N,N-dimethylbenzylamines (1a–f) at palladium, to form palladacycles di-μ-acetatobis[o-dimethylaminomethyl-n-fluorophenyl-C,N)dipalladium(II) (2a–f) and di-μ-chlorobis[o-dimethylaminomethyl-n-fluorophenyl-C,N)dipalladium(II) (3a–e), has been investigated. When fluorinated substrates with two sites available for the C–H functionalization (1c and 1e) undergo cyclopalladation via a CMD mechanism (acetate-bridged palladacycles), they do not exhibit regioselectivity. In contrast, the same substrates exhibit complete regioselectivity for the C–H functionalization para to fluorine in cyclopalladation reactions that proceed via an SEAr mechanism (involving chloride-bridged palladacycles). X-ray crystal structures were obtained for all the palladacycles synthesized, and a structural analysis showed that the number and the position of the fluorine atoms on the aromatic ring have a marked effect on the “...
Databáze:	OpenAIRE
Externí odkaz:	https://explore.openaire.eu/search/publication?articleId=doi_________::9cc38246aa02bece397a798abe38872b https://doi.org/10.1021/acs.organomet.5b00608 Zobrazit plný text záznamu