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Efficient Synthesis of All-Carbon Quaternary Centers via the Conjugate Addition of Functionalized Monoorganozinc Bromides
Published on: May 26, 2019
A Domino Process toward Functionally Dense Quaternary Carbons through Pd-Catalyzed Decarboxylative C(sp3)-C(sp3) Bond
Wusheng Guo1, Rositha Kuniyil1, José Enrique Gómez1
1Institute of Chemical Research of Catalonia (ICIQ) , Barcelona Institute of Science and Technology , Av. Països Catalans 16 , 43007 Tarragona , Spain.
Abstract:
An efficient protocol was developed to construct functionally dense quaternary carbons with concomitant formation of a new Csp3-Csp3 bond via Pd-catalyzed decarboxylative transformation of vinyl cyclic carbonates. This redox-neutral catalytic system features stereocontrolled formation of multisubstituted allylic scaffolds with an aldehyde functionality generated in situ, and it typically can be performed at room temperature without any additives. DFT calculations provide a rationale toward the selective formation of these compounds and reveal a complex mechanism that with the help of microkinetic models is able to reproduce the nontrivial dependence of the identity of the product on the nature of the substituents in the substrate.
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