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 garner...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.展开更多
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.
文摘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.
