Computational exploration of Pd‐catalyzed C–H bond activation reactions

Abstract

Quantum chemistry is widely used to the mechanistic studies of organic and organometallic reactions. In this Review, we described the various mechanisms of palladium‐catalyzed C–H bond activation reactions, including oxidative addition, σ‐bond metathesis, 1,2‐addition, electrophilic aromatic substitution, concerted metalation‐deprotonation (CMD), and Heck‐type mechanism. The different CMD models with acetate as the base, with amidate as the base, and with the bimetallic complex are also highlighted.

Computational Study of Tandem C-C Coupling and C-H Activation Reaction of a Flexible Substrate

“…The C-H activation is the important and rate determing step in the catalytic cycle. [38][39][40][41][42] In our calculations also this step (step E in Figure 3) has the highest step-wise activation barriers, ~27 kcal mol -1 , among all the other steps calculated so far (Table 7).…”

“…This can occur directly from the d intermediates formed by the 5-exo cyclization. The other possibility is the base assisted (or concerted metalation-deprotonation) [38][39][40] pathway. We discuss these two possibilites below.…”

A noncovalent interaction insight onto the concerted metallation deprotonation mechanism

“…The so-called CMD (or AMLA) mechanism entails three key steps of lower energy payload than the alternative scenario involving an oxidative-addition step of the C-H bond to the metal center. 3,5,38 The first step entails the coordination of the "directing group", here a N,N-dimethylamino group, acting as a ligand giving rise assumably to a so-called "anagostic" intermediate, noted anag (Scheme 1), where the C-H bond to be activated is generally positioned at ca.…”

Quantum‐classical transition equation with complex trajectories

“…For example, complex quantum trajectories determined from the analytical form of the wave function have been analyzed for several stationary and nonstationary state problems. [17][18][19][20][21][22][23][24][25][26][27][28][29][30][31][32] Quantum interference demonstrated by the head-on collision of two Gaussian wave packets has been explored in the complex plane. [33][34][35] Several studies have been dedicated to issues concerning the probability density in complex space and probability conservation along complex quantum trajectories.…”