36839-95-9Relevant articles and documents
Synthesis of Polycyclic Furan and Chromene Derivatives via Cascade Reactions Enabled by Cleavage of Multiple C(sp3)?F Bonds
Xie, Ting,Zhang, Chen,Zhang, Si-Xuan,Rao, Weidong,Xu, Haiyan,Shen, Zhi-Liang,Chu, Xue-Qiang
supporting information, p. 4736 - 4743 (2020/09/23)
The strong and unreactive C?F bond makes polyfluorocarbons extremely long-lived and potentially toxic. A successive selective and controllable C(sp3)?F functionalization of polyfluoroalkylated ketones with S- and O-nucleophiles to enable efficient synthesis of pharmaceutically important fluorine- and sulfur-containing polycyclic furan and chromene derivatives under transition metal-free conditions is demonstrated here. The combination of C?S/C?O coupling, aromatization, and cyclization cascade contribute to the accurate four/five C(sp3)?F bond cleavage at two different sites of perfluoroalkyl chain. The formation of reactive quinoid intermediates and the necessity of using TBAB (tetrabutylammonium bromide) as additive and Cs2CO3 as base were identified by detailed mechanistic studies. (Figure presented.).
Radical Desulfur-Fragmentation and Reconstruction of Enol Triflates: Facile Access to α-Trifluoromethyl Ketones
Su, Xiaolong,Huang, Honggui,Yuan, Yaofeng,Li, Yi
supporting information, p. 1338 - 1341 (2017/01/24)
We report an efficient oxidative radical desulfur-fragmentation and reconstruction of enol triflates for the synthesis of α-CF3ketones. Preliminary mechanistic studies disclosed that oxidative fragmentation to release a CF3radical fr
PMHS-mediated couplings of alkynes or benzothiazoles with various electrophiles: Application to the synthesis of (-)-akolactone A
Gallagher, William P.,Maleczka Jr., Robert E.
, p. 6775 - 6779 (2007/10/03)
Polymethylhydrosiloxane (PMHS) in combination with CsF facilitates the cross-coupling of alkynes or benzothiazoles with an array of vinyl, styryl, and aryl halides or nonaflates as well as acid chlorides. Experimental and spectroscopic evidence indicates that these reactions involve the in situ generation of a siloxyl intermediate. These cross-couplings proceed relatively quickly at room temperature and under amine-free conditions. To demonstrate the applicability of the method, a total synthesis of the cyctotoxic butanolide (-)-akolactone A was carried out.