钯催化烯烃的不对称Aza-Wacker反应:高效合成手性1,3-噁嗪烷-2-酮  

Asymmetric Palladium-Catalyzed Aza-Wacker Reaction of Alkenes:Efficient Synthesis of Chiral 1,3-Oxazinan-2-ones

作　　者：杨新拓 陈品红[1] 刘国生[1,2] Yang Xintuo;Chen Pinhong;Liu Guosheng(State Key Laboratory of Organometallic Chemistry and Shanghai Hongkong Joint Laboratory in Chemical Synthesis,Center for Excellence in Molecular Synthesis,Shanghai Institute of Organic Chemistry,University of Chinese Academy of Sciences,Chinese Academy of Sciences,Shanghai 200032;Chang-Kung Chuang Institute,East China Normal University,Shanghai 200062)

机构地区：[1]中国科学院上海有机化学研究所,金属有机化学国家重点实验室,沪港化学合成联合实验室分子合成科学卓越创新中心,中国科学院大学,上海200032 [2]华东师范大学,庄长恭研究所,上海200062

出　　处：《有机化学》2022年第10期3382-3389,共8页Chinese Journal of Organic Chemistry

基　　金：国家重点研发计划(No.2021YFA1500050);国家自然科学基金(Nos.21971255,91956202,21790330,21821002);中国科学院前沿科学重点研究计划(No.QYZDJSSW-SLH055);中国科学院国际伙伴计划(No.121731KYSB20190016)资助项目。

摘　　要：报道了以氨基甲酸酯为氮亲核试剂的钯催化烯烃的分子内不对称aza-Wacker反应.该反应利用C-6位丙基取代的吡啶噁唑啉为手性配体,苯醌(BQ)为氧化剂,以良好到优秀的产率、优秀的对映选择性实现了手性1,3-噁嗪烷-2-酮类化合物的高效合成,机理研究表明反应通过烯烃的分子内不对称胺钯化启动,继而发生烷基钯的β-氢消除得到目标产物.A Pd-catalyzed asymmetric aza-Wacker-type reaction with N-Ts carbamate as the nucleophile has been developed,which employed a C-6 substituted pyridinyl-oxazoline as the chiral ligand and benzoquinone(BQ) as the oxidant. This reaction provides an efficient access to chiral 1,3-oxazinan-2-ones with good efficiency and excellent enantioselectivity. Mechanistic studies indicated that the reaction is initiated by an intramolecular asymmetric aminopalladation.

关 键 词：氮杂Wacker反应 钯催化 不对称胺钯化 手性1 3-噁嗪烷-2-酮 手性吡啶噁唑啉 

分 类 号：O626[理学—有机化学]