Competing Regiochemical Pathways in the Heck Arylation of 1,2-Dihydronaphthalene

Mild and selective base-free C–H arylation of heteroarenes: experiment and computation

“…Intermediate Int1 may alternatively undergo a Heck-type carbopalladation reaction. 28 Our calculations suggest this process to be energetically feasible, being characterized by a relatively facile free energy barrier of 17.5 kcal mol –1 ( Fig. 2 ).…”

Interplays between Reactions within and without the Catalytic Cycle of the Heck Reaction as a Clue to the Optimization of the Synthetic Protocol

“…[34][35][36][37][38] It is caused by the absence of experimental evidence of the Pd hydride formation in a model 29,30 (low temperature, low substrate/ catalyst ratio) as in real catalytic conditions. 32,33 In addition, selectivity peculiarities of the competitive reactions (with two alkenes) 37,38 and non-competitive (regular) reactions 36 have become a basis for several alternative mechanistic scenarios proposed for the step of the arylation product formation (D), including bimolecular reaction of s-alkyl Pd complex with the base [34][35][36] or initial alkene. 37,38 However, there are unequivocally established facts that are not taken into account by the traditional mechanism of the catalytic cycle.…”

Well‐Defined and Robust Rhodium Catalysts for the Hydroacylation of Terminal and Internal Alkenes

“…The dihydrofuran reaction represents a formal trans H-elimination from the insertion intermediate. [22] Interestingly, when [D]- 4 a and cyclooctene were subjected to catalytic conditions, no turnover was detected, but selective H/D exchange at the alkene, alongside [H]- 4 a , was observed. This unexpected selectivity hints at a richer mechanistic landscape with these substrates that warrants further detailed investigation.…”