Tu Wenbin, Farndon Joshua J, Robertson Craig M, Bower John F
Department of Chemistry, University of Liverpool, Crown Street, Liverpool, United Kingdom, L69 7ZD.
School of Chemistry, University of Bristol, Cantock's Close, Bristol, United Kingdom, BS8 1TS.
Angew Chem Int Ed Engl. 2024 Dec 2;63(49):e202409836. doi: 10.1002/anie.202409836. Epub 2024 Oct 18.
Under acidic conditions (TFA) and in the presence of water, BocNHOTs promotes stereospecific 1,2-aminohydroxylations of alkenes. The processes involve intermolecular aza-Prilezhaev aziridination followed by stereospecific S2 opening by water. This reagent combination provides regiochemical outcomes that are opposite to, or more selective than those observed using epoxidation initiated 1,2-aminohydroxylation protocols. Replacement of water by other nucleophiles allows 1,2-amino(thio)etherification, diamination, aminoazidation and aminofluorination reactions. Intramolecular processes are also feasible, including unusual variants that evoke azabicyclobutane-like reactivity.
在酸性条件下（三氟乙酸）且有水存在时，BocNHOTs可促进烯烃的立体专一性1,2 - 氨基羟基化反应。该过程涉及分子间氮杂 - 普列谢耶夫氮丙啶化反应，随后水进行立体专一性的SN2开环反应。这种试剂组合提供的区域化学结果与通过环氧化引发的1,2 - 氨基羟基化方案所观察到的结果相反，或更具选择性。用其他亲核试剂替代水可实现1,2 - 氨基（硫）醚化、双胺化、氨基叠氮化和氨基氟化反应。分子内反应也是可行的，包括引发类似氮杂双环丁烷反应性的异常变体。
