Synthesis of Complex Eneynes by Selective α and β C−H Alkynylation of Aryl Alkenes
Xiandie Zhang , Liu Xiuying , Liuyan Li , Jingwen Li , Li Zhao , Rui He , Chao Shen , Guofu Zhong , Jian Zhang
Chinese Journal of Chemistry ›› 2025, Vol. 43 ›› Issue (24) : 3569 -3574.
Eneyne is one of the most prevalent building blocks in synthetic chemistry. Alkenyl C−H alkynylation affords an efficient synthesis of eneynes, however, the direct use of styrenes as the synthon has remained much unexplored so far. We present the first α-/β-C−H alkynylation of E- and Z aryl alkenes as well as α-substituted aryl alkenes, producing complex eneynes with excellent regio- and E/Z ratio selectivity, assisted by N,N-bidentate directing group under palladium catalysis. Notably, disubstituted E-aryl alkenes underwent α-C−H alkynylation and then β-C−H alkenylation to produce conjugated dieneynes. The robustness of the protocol was further demonstrated by the successful C−H conversion of substrates including 2-alkenyl benzyl amides and anilides, proceeding by five- to seven-membered endo-/exo-palladacycles.
Eneyne / Alkynylation / Alkenylation / C−H activation / Aryl alkenes / Alkyne / Benzyl amine / Aniline
2025 SIOC, CAS, Shanghai, & WILEY-VCH GmbH
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