Key Laboratory of Molecular Target & Clinical Pharmacology and State Key Laboratory of Respiratory Disease, School of Pharmaceutical Sciences & the Fifth Affiliated Hospital , Guangzhou Medical University , Guangzhou , Guangdong 511436 , China.
School of Chemical Engineering and Technology , Sun Yat-sen University , Guangzhou , Guangdong 510275 , China.
Org Lett. 2019 Jul 5;21(13):5229-5233. doi: 10.1021/acs.orglett.9b01831. Epub 2019 Jun 26.
An efficient and practical Rh(III)-catalyzed redox-neutral [4 + 1] annulation of N-phenoxy amides with α, α-difluoromethylene alkynes has been realized to give direct access to the Z-configured monofluoroalkenyl dihydrobenzo[ d]isoxazole framework with broad substrate compatibility and good functional group tolerance, which was further enhanced by the late-stage C-H modification of complex bioactive compounds. Subsequent density functional theory calculations revealed that the stereoselective β-F elimination involving an allene species played a decisive role in determining the reaction outcome and such Z-selectivity.
一种高效实用的 Rh(III)催化的氧化还原中性[4+1]环化反应，实现了 N-苯氧基酰胺与α,α-二氟亚甲基炔的直接环化，得到了 Z-构型的单氟烯基二氢苯并[d]异恶唑骨架，具有广泛的底物兼容性和良好的官能团容忍性，进一步通过复杂生物活性化合物的晚期 C-H 修饰得到增强。随后的密度泛函理论计算表明，涉及丙二烯物种的立体选择性β-F 消除在决定反应结果和这种 Z-选择性方面起着决定性的作用。
