Moon Hye Won, Lavagnino Marissa N, Lim Soohyun, Palkowitz Maximilian D, Mandler Michael D, Beutner Gregory L, Drance Myles J, Lipshultz Jeffrey M, Scola Paul M, Radosevich Alexander T
Department of Chemistry, Massachusetts Institute of Technology, Cambridge, Massachusetts 02139, United States.
Small Molecule Drug Discovery, Bristol Myers Squibb, 250 Water Street, Cambridge, Massachusetts 02141, United States.
J Am Chem Soc. 2023 Oct 18;145(41):22735-22744. doi: 10.1021/jacs.3c08373. Epub 2023 Oct 9.
A method for deoxyfluorination of aliphatic primary, secondary, and tertiary alcohols is reported, employing a nontrigonal phosphorus triamide for base-free alcohol activation in conjunction with an organic soluble fluoride donor and a triarylborane fluoride shuttling catalyst. Mechanistic experiments are consistent with a reaction that proceeds by the collapse of an oxyphosphonium fluoroborate ion pair with fluoride transfer. The substrate scope complements existing deoxyfluorination methods and enables the preparation of homochiral secondary and tertiary alkylfluorides by stereoinversion of the substrate alcohol.
报道了一种脂肪族伯醇、仲醇和叔醇的脱氧氟化方法，该方法使用一种非三角磷三酰胺在无碱条件下活化醇，同时结合一种有机可溶性氟供体和一种三芳基硼烷氟穿梭催化剂。机理实验与通过氧鎓氟硼酸根离子对的分解并伴随氟转移而进行的反应一致。底物范围补充了现有的脱氧氟化方法，并能够通过底物醇的立体反转制备手性纯的仲烷基氟化物和叔烷基氟化物。
