Radical-mediated reactions have many advantages in the construction of complex molecular scaffolds by forging chemical bonds of high challenge.Diazenes,including 1,1-diazenes and 1,2-diazenes,can generate biradical sp...Radical-mediated reactions have many advantages in the construction of complex molecular scaffolds by forging chemical bonds of high challenge.Diazenes,including 1,1-diazenes and 1,2-diazenes,can generate biradical species via nitrogen extrusion under thermal or photochemical conditions.The superior reactivity of the generated biradical enables various types of synthetic transformations with excellent chemoselectivity and has been applied to the complex natural products synthesis.In this mini-review,the modes of reaction are summarized and discussed,namely ring contraction via nitrogen deletion,homo or heterodimerization,trimethylenemethane(TMM)-diyl cycloaddition.Applications of these classes of reactions in complex natural product synthesis are illustrated.Last but not least,the current state,future directions,and opportunities for dinitrogen extrusion reaction from diazenes are highlighted and discussed.展开更多
An efficient synthetic route to muurolane type sesquiterpenes starting from （R）-carvone, employing allylic diazene rearrangement and the ring closing methesis （RCM） reaction as key steps, is described. The first a...An efficient synthetic route to muurolane type sesquiterpenes starting from （R）-carvone, employing allylic diazene rearrangement and the ring closing methesis （RCM） reaction as key steps, is described. The first asymmetric total synthesis of （-）-10α- hydroxy-4-muurolen-3-one 11 and （-）-10β-hydroxy-4-muurolen-3-one C was accomplished. Through the total synthesis, the absolute configurations of the natural products A, B and C were established.展开更多
基金Fuzhou University for the funding support(No.GXRC21051)the Award Program for Minjiang Scholar Professorship。
文摘Radical-mediated reactions have many advantages in the construction of complex molecular scaffolds by forging chemical bonds of high challenge.Diazenes,including 1,1-diazenes and 1,2-diazenes,can generate biradical species via nitrogen extrusion under thermal or photochemical conditions.The superior reactivity of the generated biradical enables various types of synthetic transformations with excellent chemoselectivity and has been applied to the complex natural products synthesis.In this mini-review,the modes of reaction are summarized and discussed,namely ring contraction via nitrogen deletion,homo or heterodimerization,trimethylenemethane(TMM)-diyl cycloaddition.Applications of these classes of reactions in complex natural product synthesis are illustrated.Last but not least,the current state,future directions,and opportunities for dinitrogen extrusion reaction from diazenes are highlighted and discussed.
基金the financial supports from the National Natural Science Foundation of China (No.20272021).
文摘An efficient synthetic route to muurolane type sesquiterpenes starting from （R）-carvone, employing allylic diazene rearrangement and the ring closing methesis （RCM） reaction as key steps, is described. The first asymmetric total synthesis of （-）-10α- hydroxy-4-muurolen-3-one 11 and （-）-10β-hydroxy-4-muurolen-3-one C was accomplished. Through the total synthesis, the absolute configurations of the natural products A, B and C were established.
