Catalytic Enantioselective Synthesis Enabled by Electrochemistry

Abstract

Catalytic enantioselective electrochemical synthesis has emerged in recent years as an efficient, clean, sustainable way to obtain chiral, non-racemic molecules. The difficulties in finding reaction conditions that are compatible with the delicate functional groups of many chiral ligands and organocatalysts has hampered the developments in this field. However, the fact that very minute differences in potential can be selected, allows for fine-tuning, so that very high chemoselectivities can be achieved, which is attracting much attention. Although still few in number compared to other areas of knowledge, the existing methods allow a variety of bond-forming reactions to be performed, and very high yields and ees can be achieved. The present review surveys the literature published in the last four years. 1. Introduction 2. Transition metal catalyzed reactions 2.1 Alkylation by C-H bond functionalization: C(sp3)-C(sp3) bond formation 2.2 C(sp3)-C(sp2) bond formation 2.2.1 Alkene functionalization by cross-coupling reactions 2.2.2 Arylation by cross-coupling reactions 2.3 Alkynylation: C(sp3)-C(sp) bond formation 2.4 Cross-coupling reactions for the synthesis of axially chiral biaryls 2.5 Cyanofunctionalization 2.6 Miscellaneous 3. Organocatalysis 4. Conclusions

Enantioselective Synthesis of Heteroatom‐Linked Non‐Biaryl Atropisomers

“…Finally, the atroposelectivity around a C−B [48] bond has been tackled very recently [49] and compiled in a recent article, [50] but unlike the different approaches detailed in the present review, the boron atom is included in a cycle and the enantiomerization of these compounds necessitates the rotation around on single C−B bond.…”

Enantioselective cross-dehydrogenative coupling enabled by organocatalysis

“…[73][74][75][76][77][78][79][80][81][82][83][84][85] Particularly, in recent years, the combination of organocatalysis and transition metal catalysis or the synergy of organocatalysis and photocatalysis or electrocatalysis has been demonstrated as an efficient fashion to realize a series of enantio-selective CDC reactions, expanding the scope and potential of this field. [70][71][72][86][87][88][89][90][91][92][93][94][95][96][97][98] Two comprehensive reviews were published seven years ago on the topic of C-H functionalization through organocatalysis. 70,71 However, there is no reviews focusing on organocatalytic CDC reactions despite its significance.…”

“…73–85 Particularly, in recent years, the combination of organocatalysis and transition metal catalysis or the synergy of organocatalysis and photocatalysis or electrocatalysis has been demonstrated as an efficient fashion to realize a series of enantioselective CDC reactions, expanding the scope and potential of this field. 70–72,86–98…”

Electrochemical Organic Synthesis

“…4 Phillips, Pombeiro, and associates encapsulate the power of electrochemistry in catalytic enantioselective synthesis. 5 Zhang, Liu, and their team offer a comprehensive summary of electrochemical cascade cyclization reactions used in carbon ring and heterocycle production. 6 Mo and his team succinctly overview the latest breakthroughs in high-throughput experimentation technology for electrosynthesis.…”