Chapter 20. Ar-C bond formation by aromatic carbon-carbon ipso-substitution reaction

FAGNONI MAURIZIO; BONESI SERGIO M

Arene Chemistry: Reaction Mechanisms and Methods for Aromatic Compounds

Wiley and Sons

Lugar: New Jersey; Año: 2016; p. 615 - 640

The use of metal-mediated reactions is nowadays recognized as the best approach for the formation of an Ar-C bond, a key reaction for the synthesis of valuable compounds (please see Chapters 17-19 of this book) [1]. This process involves the metal-catalyzed cross-coupling reaction between an electrophilic aromatic (Ar-X, mainly an aryl halide or an aryl sulfonate) and a carbon based nucleophile (Nu-Y, Scheme 20-1). The driving force of these ipso-substitution reactions is the formation of an Ar-C bond at the expenses of a weaker Ar-X bond (X ≠ H). However, in the last years various C-based leaving groups including carbinol, CN, COOH(COOR), CO-X-CO (X = O, NR, S) and carbonyl groups have been developed and used in arylation reactions [2,3]. We dubbed here such a process as the ARomatic Carbon-carbon Ipso-Substitution (ARCIS) reaction (Scheme 20-1).Various ARCIS reactions will be then collected here according to the Ar-C bond formed in particular for the preparation of alkyl substituted, vinyl, and alkynyl aromatics as well as biphenyls.