通过催化硝基亚乙烯基的氨溴化反应，无需使用色谱和重结晶，即可获得邻位叔丁氧羰基氨基二溴化物。
Approach to vicinal t-Boc-amino dibromides via catalytic aminobromination of nitrostyrenes without using chromatography and recrystallization.
机构信息
School of Chemistry and Chemical Engineering, Nanjing University, Nanjing 210093, P. R. China.
出版信息
J Org Chem. 2013 Feb 1;78(3):1171-5. doi: 10.1021/jo302727v. Epub 2013 Jan 23.
Abstract
A 1.0 mol % amount of K(3)PO(4)·3H(2)O was found to catalyze aminohalogenation reaction of nitrostyrenes with N,N-dibromo-tert-butylcarbamate (t-Boc-NBr(2)) in a dichloroethane system. Good to excellent yields and complete regioselectivity have been achieved by taking advantage of the GAP workup without using traditional purification techniques such as column chromatography and recrystallization. Anew mechanism is proposed involving radical and ionic catalytic cycles and an intramolecular migration.
摘要
在二氯乙烷体系中，发现 1.0 mol%的 K(3)PO(4)·3H(2)O 可以催化硝基亚乙烯与 N,N-二溴叔丁基氨基甲酸酯（t-Boc-NBr(2)) 的氨卤化反应。通过利用 GAP 后处理，而不使用传统的纯化技术（如柱层析和重结晶），可以获得良好至优异的产率和完全的区域选择性。提出了一种新的机制，涉及自由基和离子催化循环以及分子内迁移。
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