Cu-Catalyzed Asymmetric Dicarboxylation of 1,3-Dienes with CO₂

Abstract

Dicarboxylic acids and derivatives are important building blocks in organic synthesis, biochemistry, and the polymer industry. Although catalytic dicarboxylation with CO 2 represents a straightforward and sustainable route to dicarboxylic acids, it is still highly challenging and limited to generation of achiral or racemic dicarboxylic acids. To date, catalytic asymmetric dicarboxylation with CO 2 to give chiral dicarboxylic acids has not been reported. Herein, we report the first asymmetric dicarboxylation of 1,3-dienes with CO 2 via Cu catalysis. This strategy provides an efficient and environmentally benign route to chiral dicarboxylic acids with high regio-, chemo-, and enantioselectivities. The copper self-relay catalysis, that is, Cu-catalyzed boracarboxylation of 1,3-dienes to give carboxylated allyl boronic ester intermediates and subsequent carboxylation of C−B bonds to give dicarboxylates, is key to the success of this dicarboxylation. Moreover, this protocol exhibits broad substrate scope, good functional group tolerance, easy product derivatizations, and facile synthesis of chiral liquid crystalline polyester and drug-like scaffolds.

Asymmetric Boracarboxylation of Styrenes Using Carbon Dioxide

“…of > 99:1. [23] The group of Zhou and Tang reported a Cu-catalysed boracarboxylation of styrenes using a chiral NHCÀ Cu catalyst providing excellent enantioselectivities up to e.r. > 98:2 for electron-rich substrates.…”

Electrochemical E-Selective Semireductive Dicarboxylation of Aryl Alkynes with CO2

“…Dicarboxylic acids are attractive structural motifs in organic synthesis and have a wide application in the pharmaceutical and polymer industries (Figure A) . Recently, synthesizing dicarboxylic acids with CO 2 has attracted much concern and the thermal-, photo- and electro-mediated/catalytic methods have been developed accordingly. Although great progress has been made, the thermal-catalytic dicarboxylation with CO 2 relies on the noble metal catalysts and a stoichiometric amount of reductant, while the photocatalytic approaches suffer from the low efficiency, necessity of an excess amount of base, and expensive photosensitizer, which hampers the commercial applications.…”