不对称烯丙基化反应合成含有三苯胺核心单元的荧光非天然氨基酸衍生物  

Synthesis of Non-Natural Amino Acid Derivatives Bearing Triphenylamine Core Skeleton via Pd-Catalyzed Direct Asymmetric Allylic Alkylation

作　　者：张金龙 蒋高喜 Zhang Jinlong;Jiang Gaoxi(State Key Laboratory for Oxo Synthesis and Selective Oxidation,Center for Excellence in Molecular Synthesis,Suzhou Research Institute of LICP,Lanzhou Institute of Chemical Physics (LICP),Chinese Academy of Sciences,Lanzhou 730000)

机构地区：[1]羰基合成与选择氧化国家重点实验室中国科学院兰州化学物理研究所苏州研究院清洁合成技术部,兰州730000

出　　处：《化学学报》2018年第11期890-894,共5页Acta Chimica Sinica

基　　金：国家自然科学基金(No.21602231);江苏省自然科学基金(No.BK20160396)资助~~

摘　　要：报道了一种钯催化噁唑酮和烯丙醇的不对称烯丙基化反应合成相应的三苯胺核心非天然氨基酸化合物的方法.反应收率高达95%,对映选择性过量值最高为97%ee.该反应操作简单,条件温和,原子经济性好,水为唯一副产物.Allylic alkylation first pioneered by Tsuji in 1965and,later adapted by Trost in 1973with the introduction of phosphine ligands represents one of the straightforward and powerful synthetic tool for new carbon-carbon formation,especially the direct asymmetric allylic alkylation (AAA)has been widely utilized in the synthesis of natural products and phar- maceutical molecules.Conventionally,AAA reactions involve activated allylic alcohol derivatives,such as carbonates, amines,acetates,and halides,which require an equivalent strong base to react with the acidic by-product and inevitably results in stoichiometric waste.From the viewpoint of environmental and atom economy,the direct use of allylic alcohol instead its derivatives is much more practical by virtue of only water being formed as a byproduct.However,one of the challenges existed in such transformations is the poor reactivity of allylic alcohol.In 2006,a breakthrough was first made by Trost group,by using stoichiometric amounts of borane as the critical promoter in the direct AAA reaction of indoles with allylic alcohols.Afterwards,List,Gong,and Zhang reported independently the significant achievements applying aldehyde, pyrazol-5-ones,and ketones as nucleophiles,respectively.In 2004,our group enclosed the Bronsted acid accelerated Pd-catalyzed direct asymmetric allylic alkylation of azlactones with simple allylic alcohols.On the other hand,triphenylamine (TPA)as a strong electron-donating and oxidative stable molecule has been extensively utilized in the new organic elec- troluminescent materials,special dye synthesis and organic solar cells.Considering the impressive fluorescence emission ability of TPA and basing on these pioneering works,we reasoned that the direct connection of the TPA substructure with amino acid molecules could give rise to the fluorescence emission compounds.Thus,we report here the first installation of the non-natural amino acid derivatives bearing TPA core skeleton via Pd-catalyzed direct AAA reaction and the desired prod-ucts were

关 键 词：不对称烯丙基化 非天然氨基酸 三苯胺 原子经济性 

分 类 号：O621.251[理学—有机化学]