Visible‐Light‐Enabled Carboxylation of Benzyl Alcohol Derivatives with CO₂ Using a Palladium/Iridium Dual Catalyst

Abstract

Invited for this month′s cover is the group of Nobuharu Iwasawa at Tokyo Institute of Technology. The image shows a switchable site‐selective carboxylation between benzylic C−O and aryl C−Cl moieties enabled by a palladium/iridium dual catalyst under visible light irradiation. The Communication itself is available at 10.1002/cssc.202102095.

Recent advancements in visible-light-driven carboxylation with carbon dioxide

“…Late in 2021, Iwasawa and co-workers reported the efficient carboxylation of benzyl alcohol derivatives with CO 2 through photoredox/Pd dual catalysis (Scheme 21). 35 Benzylic carbonates were used in this protocol as substituents for benzyl alcohols, affording benzylic carboxylic acids in moderate to high yields. A plausible mechanism was proposed based on their previous work, in which the oxidative addition of benzylic C–O bonds to Pd(0) ensured that the catalytic cycle proceeded smoothly.…”

Recent Advances in Light‐Induced Carboxylation of Organic (Pseudo)Halides with CO2

“…Very recently, Iwasawa's group extended the light/metal dual-catalyzed carboxylation of CÀ O electrophiles to esters with higher CÀ O bond dissociation energy (Scheme 15). [19] The protocol was applicable not only to benzyl carbonates, but also to esters, a carbamate, and even a diethylphosphate. Moreover, the presence of substitution groups at α-position did not hamper the yield, allowing the synthesis of anti-inflammatory drug Naproxen in high yield.…”

Recent Advances in Photocatalytic Carboxylation with CO2 via σ-Bond Cleavage

“…2022 年, Iwasawa 课题组 [21] [25] . 季铵盐是一类高效的亲电试剂, 很容易从胺类 化合物制得, 被广泛应用于过渡金属催化的与各种有机 金属化合物(有机镁、硼、锌、锂、锡和铝)的交叉偶联 反应中 [26] .…”