Guo Junkai, Kuang Cuiwen, Rong Jian, Li Lingchun, Ni Chuanfa, Hu Jinbo
Key Laboratory of Organofluorine Chemistry, Center for Excellence in Molecular Synthesis, Shanghai Institute of Organic Chemistry, University of Chinese Academy of Sciences, Chinese Academy of Sciences, 345 Ling-Ling Road, Shanghai, 200032, P. R. China.
Chemistry. 2019 May 28;25(30):7259-7264. doi: 10.1002/chem.201901176. Epub 2019 Apr 26.
The deoxyfluorination of alcohols is a fundamentally important approach to access alkyl fluorides, and thus the development of shelf-stable, easy-to-handle, fluorine-economical, and highly selective deoxyfluorination reagents is highly desired. This work describes the development of a crystalline compound, N-tosyl-4-chlorobenzenesulfonimidoyl fluoride (SulfoxFluor), as a novel deoxyfluorination reagent that possesses all of the aforementioned merits, which is rare in the arena of deoxyfluorination. Endowed by the multi-dimensional modulating ability of the sulfonimidoyl group, SulfoxFluor is superior to 2-pyridinesulfonyl fluoride (PyFluor) in fluorination rate, and is also superior to perfluorobutanesulfonyl fluoride (PBSF) in fluorine-economy. Its reaction with alcohols not only tolerates a wide range of functionalities including the more sterically hindered alcoholic hydroxyl groups, but also exhibits high fluorination/elimination selectivity. Because SulfoxFluor can be easily prepared from inexpensive materials and can be safely handled without special techniques, it promises to serve as a practical deoxyfluorination reagent for the synthesis of various alkyl fluorides.
醇的脱氧氟化反应是制备烷基氟化物的一种根本重要的方法，因此，人们迫切希望开发出储存稳定、易于操作、氟经济且具有高选择性的脱氧氟化试剂。本文报道了一种结晶化合物N-对甲苯磺酰基-4-氯苯磺酰亚胺氟化物（SulfoxFluor）的开发，它是一种新型的脱氧氟化试剂，具备上述所有优点，这在脱氧氟化领域中是罕见的。受磺酰亚胺基团的多维调节能力的影响，SulfoxFluor在氟化速率上优于2-吡啶磺酰氟（PyFluor），在氟经济性方面也优于全氟丁烷磺酰氟（PBSF）。它与醇的反应不仅能耐受包括空间位阻较大的醇羟基在内的多种官能团，而且还表现出高氟化/消除选择性。由于SulfoxFluor可以由廉价原料轻松制备，且无需特殊技术即可安全操作，因此有望成为合成各种烷基氟化物的实用脱氧氟化试剂。
