Due to the low reactivity of 1,6-dienes and the challenge of selectively differentiating such two olefins, the development of metal-catalyzed asymmetric cyclization of 1,6-dienes remains largely underdeveloped. Herein, we describe the first copper(I)-catalyzed asymmetric borylative cyclization of cyclohexadienone-tethered terminal alkenes (1,6-dienes) via a tandem process: the regioselective borocupration of the electron-rich terminal alkene and subsequent conjugate addition of stereospecific secondary alkyl-copper(I) to the electron-deficient cyclohexadienone, affording enantioenriched bicyclic skeletons bearing three contiguous stereocenters in all cis-form. Meanwhile, this mild catalytic protocol is generally compatible with a wide range of functional groups, which allows further facile conversion of the cyclization products.
[1]Shanghai Univ Tradit Chinese Med, Innovat Res Inst Tradit Chinese Med, Res Ctr Chiral Drugs, 1200 Cailun Rd, Shanghai 201203, Peoples R China.
[2]Shanghai Univ Tradit Chinese Med, China Thailand Joint Res Inst Nat Med, 1200 Cailun Rd, Shanghai 201203, Peoples R China.
[3]Univ Chinese Acad Sci, Chinese Acad Sci, Shanghai Inst Organ Chem, CAS Key Lab Synthet Chem Nat Subst, 345 Lingling Rd, Shanghai 200032, Peoples R China.
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