3 research outputs found
Palladium-Catalyzed Oxidative Diarylating Carbocyclization of Enynes
A mild and efficient palladium-catalyzed oxidative diarylating carbocyclization of enynes is described. The reaction tolerates a range of functionalized arylboronic acids to give diarylated products in good yields. Control experiments suggest that the reaction starts with an arylpalladation of the alkyne, followed by carbocyclization, transmetalation, and reductive elimination to afford the diarylated product
Kinetics and Mechanism of the Palladium-Catalyzed Oxidative Arylating Carbocyclization of Allenynes
Pd-catalyzed C–C
bond-forming reactions under oxidative
conditions constitute a class of important and widely used synthetic
protocols. This Article describes a mechanistic investigation of the
arylating carbocyclization of allenynes using boronic acids and focuses
on the correlation between reaction conditions and product selectivity.
Isotope effects confirm that either allenic or propargylic C–H
activation occurs directly after substrate binding. With an excess
of H<sub>2</sub>O, a triene product is selectively formed via allenic
C–H activation. The latter C–H activation was found
to be turnover-limiting and the reaction zeroth order in reactants
as well as the oxidant. A dominant feature is continuous catalyst
activation, which was shown to occur even in the absence of substrate.
Smaller amounts of H<sub>2</sub>O lead to mixtures of triene and vinylallene
products, where the latter is formed via propargylic C–H activation.
The formation of triene occurs only in the presence of ArBÂ(OH)<sub>2</sub>. Vinylallene, on the other hand, was shown to be formed by
consumption of (ArBO)<sub>3</sub> as a first-order reactant. Conditions
with sub-stoichiometric BF<sub>3</sub>·OEt<sub>2</sub> gave selectively
the vinylallene product, and the reaction is first order in PhBÂ(OH)<sub>2</sub>. Both C–H activation and transmetalation influence
the reaction rate. However, with electron-deficient ArBÂ(OH)<sub>2</sub>, C–H activation is turnover-limiting. It was difficult to
establish the order of transmetalation vs C–H activation with
certainty, but the results suggest that BF<sub>3</sub>·OEt<sub>2</sub> promotes an early transmetalation. The catalytically active
species were found to be dependent on the reaction conditions, and
H<sub>2</sub>O is a crucial parameter in the control of selectivity
Automated, Capsule-Based Suzuki–Miyaura Cross Couplings
The development of an automated process for Suzuki–Miyaura
cross couplings is described, in which the complete reaction, workup,
and product isolation are effected automatically with no user involvement,
aside from loading of the starting materials and reaction capsule.
This practical and simple method was successfully demonstrated to
provide the desired biaryl products using a range of aryl bromides
and boronic acids and is also effective for the late-stage functionalization
of aryl halides in bioactive molecules