Visible-Light-Driven Anti-Markovnikov Hydrocarboxylation of Acrylates and Styrenes with CO ₂

Abstract

Light-driven carbon dioxide (CO 2 ) capture and utilization is one of the most fundamental reactions in Nature. Herein, we report the first visible-light-driven photocatalyst-free hydrocarboxylation of alkenes with CO 2 . Diverse acrylates and styrenes, including challenging tri-and tetrasubstituted ones, undergo anti-Markovnikov hydrocarboxylation with high selectivities to generate valuable succinic acid derivatives and 3-arylpropionic acids. In addition to the use of stoichiometric aryl thiols, the thiol catalysis is also developed, representing the first visible-lightdriven organocatalytic hydrocarboxylation of alkenes with CO 2 . The UV-vis measurements, NMR analyses, and computational investigations support the formation of a novel charge-transfer complex (CTC) between thiolate and acrylate/styrene. Further mechanistic studies and density functional theory (DFT) calculations indicate that both alkene and CO 2 radical anions might be generated, illustrating the unusual selectivities and providing a novel strategy for CO 2 utilization.

Selective Electrosynthetic Hydrocarboxylation of α,β‐Unsaturated Esters with Carbon Dioxide**

“…[ 1 , 2 , 3 ] Recently Lan and Yu introduced a photochemical approach to a range of α,β‐unsaturated esters providing good yields of the corresponding β‐hydrocarboxylated products, using stoichiometric or catalytic aromatic thiols. [3a] Romo, utilizing the conditions originally reported by Jamison for the hydrocarboxylation of styrenes, [4] has shown that the photochemical hydrocarboxylation of α,β‐unsaturated esters can also be carried out under flow conditions and some of the products containing all‐carbon quaternary centers can be accessed in good to excellent yield. Additionally, they showed that these products are versatile building blocks for lactonization.…”

Visible-light photoredox-catalyzed umpolung carboxylation of carbonyl compounds with CO2

“…Therefore, a general and practical method is desirable. Inspired by recent visible-light-driven reductive carboxylations of different electrophiles with CO 2 44 – 59 , we wondered whether we could develop a general and practical strategy to achieve efficient and selective carboxylation of carbonyls with CO 2 via visible-light photoredox catalysis. Achieving such a goal requires addressing several challenges.…”

Stereodivergent synthesis of β-iodoenol carbamates with CO2viaphotocatalysis

“… 5 ) and carboxylic acids. 6 Organic carbamates constitute an important class of compounds, which are widely used in agrochemicals, 7 pharmaceuticals 8 and as intermediates in organic synthesis. 9 Traditional methods for the preparation of carbamates are mainly based on the use of toxic phosgene and its derivatives, which are environmentally unfriendly.…”