新型对映选择性氟化剂，（R）-和（S）-N-氟-3-叔丁基-7-硝基-3,4-二氢-2H-苯并[e][1,2]噻嗪1,1-二氧化物。

Novel enantioselective fluorinating agents, (R)- and (S)-N-fluoro-3-tert-butyl-7-nitro-3,4-dihydro-2H-benzo[e][1,2]thiazine 1,1-dioxides.

作者信息

Shibata N, Liu Z, Takeuchi Y

机构信息

Faculty of Pharmaceutical Sciences, Toyama Medical and Pharmaceutical University, Japan.

出版信息

Chem Pharm Bull (Tokyo). 2000 Dec;48(12):1954-8. doi: 10.1248/cpb.48.1954.

DOI:10.1248/cpb.48.1954

PMID:11145150

Abstract

Enantioselective fluorinating agents, (R)- and (S)-,N-fluoro-3-tert-butyl-7-nitro-3,4-dihydro-2H-benzo[e][1,2]thiazine 1,1-dioxides (BNBT-F, 2) are readily prepared in 3 steps from racemic 3-tert-butyl-7-nitro-3,4-dihydro-2H-benzo[e][1,2]thiazine 1,1-dioxides (5) via optical resolution and fluorination. These agents make accessible both enantiomers of optically active quaternary alpha-fluoro carbonyl compounds in modest to high enantioselectivities. X-ray crystallographic analysis of chiral 2 reveals a unique structure wherein the nitrogen atom is highly pyramidalized and fluorine occupies an axial position.

摘要

对映选择性氟化剂，即（R）-和（S）-N-氟-3-叔丁基-7-硝基-3,4-二氢-2H-苯并[e][1,2]噻嗪1,1-二氧化物（BNBT-F，2），可通过外消旋3-叔丁基-7-硝基-3,4-二氢-2H-苯并[e][1,2]噻嗪1,1-二氧化物（5）经光学拆分和氟化，分三步轻松制备。这些试剂能够以中等至高对映选择性获得光学活性季鏻α-氟代羰基化合物的两种对映体。手性2的X射线晶体学分析揭示了一种独特的结构，其中氮原子高度呈锥体状，氟占据轴向位置。