γ-Butyrolactone Synthesis from Allylic Alcohols Using the CO_(2)Radical Anion  

作　　者：Saeesh R.Mangaonkar Hiroki Hayashi Wataru Kanna Suvankar Debbarma Yu Harabuchi Satoshi Maeda Tsuyoshi Mita 

机构地区：[1]Institute for Chemical Reaction Design and Discovery(WPI-ICReDD),Hokkaido University,Sapporo,Hokkaido 001-0021,Japan [2]JST,ERATO Maeda Artificial Intelligence in Chemical Reaction Design and Discovery Project,Sapporo,Hokkaido 060-0810,Japan [3]Department of Chemistry,Faculty of Science,Hokkaido University,Sapporo,Hokkaido 060-0810,Japan [4]Research and Services Division of Materials Data and Integrated System(MaDIS),National Institute for Materials Science(NIMS),Tsukuba,Ibaraki 305-0044,Japan

出　　处：《Precision Chemistry》2024年第3期88-95,共8页精准化学（英文）

基　　金：This work was financially supported by JST-ERATO(JPMJER1903);Scientific Research(B)(22H02069);Transformative Research Areas(A)(Digitalization-driven Transformative Organic Synthesis(Digi-TOS))(22H05330).T.M.thanks the Naito Foundation for financial support.

摘　　要：γ-Butyrolactone structures are commonly found in various natural products and serve as crucial building blocks in organic synthesis.Consequently,the development of methods for synthesizingγ-butyrolactones has garnered significant interest within the organic synthesis community.In this study,we present a direct and highly efficient approach for the synthesis ofγ-butyrolactones from allylic alcohols.Notably,this study represents the first instance ofγ-butyrolactone synthesis initiated by radical hydrocarboxylation using CO_(2)^(•–),generated from metal formates,followed by cyclization.This two-step process is achieved through the synergistic interaction of photoredox and hydrogen atom transfer(HAT)catalysis,resulting in the production ofγ-butyrolactones with exceptional efficiency.Additionally,when employingα,α-diaryl allylic alcohol derivatives as substrates,the reaction involves 1,2-aryl migration,which occurs concomitantly with CO_(2)^(•–)addition,leading to the formation of 4,5-substituted lactones in a good yield.The artificial force induced reaction(AFIR)method identified the preferred 1,2-aryl migration pathway along with potential byproduct pathways,in which the targeted 1,2-migration was found to be the most plausible pathway.

关 键 词：CO_(2) LACTONE RADICAL PHOTOREDOX visible light CARBOXYLATION calculation DFT 

分 类 号：O62[理学—有机化学]