| Allyl and alkynyl compounds are not only important organic synthesis intermediates but also widespread in nature,so their synthesis research has important theoretical significance and application value.The traditional introduction methods of allyl group included Tsuji-Trost allylation and Keck free radical allylation,and the traditional introduction methods of alkyne group included Cadiot-Chodkiewicz coupling,Castro-Stephens coupling and Sonogashira coupling.Although significant progress has been made in the above methods,there are still some shortcomings such as limited substrate range,poor atom economy and harsh reaction conditions.In addition,chemists have developed free radical allylation and alkynylation reactions that focus on preactivated alkanes and simple alkane substrates,however,the direct allylation and alkynylation of the C(sp~3)-H bond in the free radical pathway are few,so it is still urgent to develop new synthetic methods.In this paper,a copper-catalyzed direct alkane intermolecular C(sp~3)-H bond alkynylation and allylation reaction has been developed.A series of allyl and alkynylated compounds were synthesized with substituted N-fluorobenzenesulfonamide as hydrogen transfer reagent and 1,10-phen as ligand catalyzed by Cu Cl under mild reaction conditions with high yields and good regioselectivities.The reaction has wide substrate scope with good functional group compatibility,and can realize the late functionalization of some natural products and drug molecules.The yield of the product did not decrease in the scale-up test,which indicates that the reaction has a good application prospect.Finally,the possible reaction mechanism was proposed by the synthesis and characterization of the intermediates and the related control experiments.This work extends the application of metal-catalyzed functionalization of the unactivated C(sp~3)-H bond and provides a novel strategy for the synthesis of allyl and alkynyl alkanes. |
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