Ontology highlight
ABSTRACT:
SUBMITTER: McCarren PR
PROVIDER: S-EPMC2824658 | biostudies-literature | 2009 May
REPOSITORIES: biostudies-literature
Journal of the American Chemical Society 20090501 19
The mechanism of nickel-catalyzed reductive alkyne-aldehyde coupling reactions has been investigated using density functional theory. The preferred mechanism involves oxidative cyclization to form the nickeladihydrofuran intermediate followed by transmetalation and reductive elimination. The rate- and selectivity-determining oxidative cyclization transition state is analyzed in detail. The d --> pi*(perpendicular) back-donation stabilizes the transition state and leads to higher reactivity for a ...[more]