钯催化的未活化烯烃的分子内氨基氟化反应。
Palladium-catalyzed intramolecular aminofluorination of unactivated alkenes.
机构信息
State Key Laboratory of Organometallics Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Science, 354 Fenglin Road, Shanghai, China, 200032.
出版信息
J Am Chem Soc. 2009 Nov 18;131(45):16354-5. doi: 10.1021/ja9076588.
A novel palladium-catalyzed intramolecular oxidative aminofluorination of unactivated alkenes has been developed, in which AgF was used as a key fluorinating reagent and PhI(OPiv)(2) as oxidant. The reaction afforded vicinal fluoroamine products with very high regioselectivity. A Pd(II/IV) catalytic cycle was proposed, and preliminary mechanistic studies indicated that direct reductive elimination of Pd(IV) intermediates is favored, albeit competing with S(N)2 nucleophilic attack by fluorine, to form a C-F bond.
一种新型的钯催化的未活化烯烃分子内氧化氨氟化反应已经被开发出来，其中 AgF 被用作关键的氟化试剂，PhI(OPiv)(2) 被用作氧化剂。该反应以非常高的区域选择性得到偕氟胺产物。提出了一个 Pd(II/IV)催化循环，初步的机理研究表明，尽管与氟的 S(N)2 亲核进攻竞争，Pd(IV)中间体的直接还原消除有利于形成 C-F 键。
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