Stereoselective Pd-Catalyzed Decarboxylative Allylation: Assembly of Highly Functionalized Allylic Amines Bearing a Quaternary Center

Abstract

Here, we report a practical and reliable methodology to direct construction of tri- and tetrasubstituted olefins bearing an allylic amine, with the concomitant construction of the sterically congested quaternary stereocenter through stereoselective palladium-catalyzed cascade decarboxylation of vinyloxazolidinones.

Pd-Catalyzed Decarboxylative Cycloaddition for the Synthesis of Highly Substituted δ-Lactones and Lactams

“…First, we investigated a model vinyl cyclic carbonate to determine the feasibility of forming the corresponding lactone products via the Pd-catalyzed decarboxylative cycloaddition process (Table ). In preliminary experiments, vinyl cyclic carbonate 1a and the general ligand 1,3-bis­(diphenylphosphino)­propane were exposed to a CO atmosphere under balloon pressure. , …”

“…In this context, many efficient Pd-catalyzed decarboxylation conversions have been reported by Zhang, Kleij, Zhao, and Glorius (Scheme b). We recently reported a Pd-catalyzed allylation to construct allylic amines and alcohols bearing an all-carbon quaternary center. , Herein, we report a practical and reliable strategy for the generation of substituted δ-lactones and lactams through a Pd-catalyzed decarboxylative cycloaddition process (Scheme c). This method successfully forms a C–O and a C–N bond in addition to installing a tetra-substituted double bond that may be further functionalized.…”

Recent Advances in the Synthesis and Ring‐Opening Transformations of 2‐Oxazolidinones

“…described an unprecedented stereoselective palladium‐catalyzed decarboxylation of N ‐protected vinyl oxazolidinones 199 to generate polysubstituted allylic amines 200 bearing a tertiary or quaternary center (Scheme 62). [103] After the optimization of the reaction conditions, tri‐ and tetrasubstituted oxazolidinones bearing a vinyl group with a different protecting group were explored. Gratifyingly, substrates with a sulfonyl protecting group gave good stereoselectivities and yields of 82–87%.…”

Pd‐catalyzed decarboxylative [3 + 2] cycloaddition: Assembly of highly functionalized spirooxindoles bearing two quaternary centers

“…At present, we have achieved a stereoselective decarboxylative allylation to generate highly substituted allylic amines bearing a quaternary center via palladium catalysis. [17] We also have reported an efficient Pdcatalyzed domino decarboxylation/carbonylation/cyclization process of VECs for the synthesis of diverse lactones and lactams. [18] In recent years, we have designed practical and reliable methodology methods for the formation of highly functionalized skeletons.…”