om6b00646_si_002.xyz (331.33 kB)
DFT Study on Rhodium-Catalyzed Intermolecular [2 + 2] Cycloaddition of Terminal Alkynes with Electron-Deficient Alkenes
dataset
posted on 2016-09-30, 19:33 authored by Liu Zhao, Lei Zhang, De-Cai FangDensity
functional theory (DFT) calculations with the B3LYP functionals
elucidated the reactivity, selectivity, and mechanisms of a rhodium-catalyzed
intermolecular [2 + 2] cycloaddition of terminal alkynes with electron-deficient
alkenes. The most plausible reaction pathway was discussed as three
distinct processes in full catalytic cycles, including (1) substrate
exchange, (2) nucleophilic addition and cyclization, and (3) separation
of product and recycling of catalyst; the formal [2 + 2] cycloaddition
indeed proceeded through a rate-determining and stepwise addition–cyclization
process. We then compared the outer-sphere and inner-sphere mechanisms
for the formation of cyclobutene intermediates and reported that the
former pathway is more accessible kinetically and thus more competitive,
being contrary to the proposed mechanism for some nickel-catalyzed
cycloaddition reactions in the literature. Furthermore, the substituent
effect has been investigated using various alkenes CH2CHR
(R = COOMe, CN, H, CH3) as reaction partners, which disclosed
that the reaction pathway for electron-deficient alkenes was mediated
by a zwitterion intermediate, whereas that for electron-neutral alkenes
was characterized as a diradical-like mechanism with an inaccessible
free-energy barrier of more than 46 kcal mol–1.
In addition, the effects of ligand and base have been discussed in
detail from the perspective of Houk’s distortion/interaction
model, providing a valuable case study for understanding the roles
played by different phosphine ligands and additives.