An enantioselective consecutive cyclization/coupling process, catalyzed by palladium is reported. Stereoinduction arises from an enantioselective carbopalladation, generating an intermediate which promotes a nucleopalladation step. The dual cyclization sequence was compatible with a variety of alkyne‐tethered oxygen‐ and nitrogen‐centered nucleophiles, and a variety of alkenyl‐tethered aryl iodides, to forge numerous bisheterocycles in good yields and high regio‐ and enantioselectivities.
A method for the palladium-catalyzed disilylation and digermanylation of aryl halides bearing a tethered alkene has been developed. The mechanism is thought to proceed via Heck-type cyclization, followed by C−H activation, resulting in a reactive fusedpalladacycle. A wide variety of disilylated and digermanylated heterocycles are obtained from readily available aryl halides in high yields with various functional groups. Moreover, the developed protocol proved to be highly diastereoselective.
A diastereo-and enantioselective synthesis of boron-containing cyclobutanols is reported. We exploit an enantioselective borylcupration to generate a chiral benzylic copper intermediate that is intercepted with a proximally tethered ketone. The scaffolds contain an all-carbon quaternary center with a modular boronate moiety which allows access to a variety of synthetically valuable functional groups. This work represents an asymmetric approach to monocyclic cyclobutanols and highlights the utility of copper catalysis in the generation of small-sized rings.
Hexafluoroisopropanol (HFIP) was employed as an additive for the generation of 3‐(chloromethylene)oxindoles via the chloroacylation of alkyne‐tethered carbamoyl chlorides. This reaction avoids the use of a metal catalyst and accesses products in high yields and stereoselectivities. Additionally, this reaction is scalable and proved amenable to a series of product derivatizations, including the synthesis of nintedanib. The reactivity of alkene‐tethered carbamoyl chlorides with hexafluoroisopropanol (HFIP) was harnessed towards the synthesis of 2‐quinolinones.
The synthesis of a broad variety
of hetero- and carbocyclic scaffolds
via a Pd-catalyzed domino Heck/SO2 insertion reaction is
reported. This reaction utilizes DABSO, a safe and easy-to-handle
alternative to SO2 gas. The reaction proceeds through a
sulfinate intermediate, which can act as a lynchpin for the in situ generation of sulfones, sulfonamides, and sulfonyl
fluorides. Good yields and scalability are demonstrated.
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