H2O2等氧化剂或助剂对Wittig类试剂的偶联二聚新反应或独特亲核性的调控及其在功能分子合成中的应用

The conventional reaction of the classic Wittig reagent (RCH = PPh3) to attack the carbonyl group to form the olefins is well known, but the oxidative coupling dimerization is rarely reported, and other catalysts or additives regulate their unconventional reactions is relatively weak or lacking the extensive research. Recently, in this laboratory it was found that the chem-green reagent H2O2 can oxidize the Wittig reagent to produce the olefins via the C-C coupling dimerization, and multiply its main structure space and molecular weight, also the Wittig reagent can attack the no-carbonyl position to form some special nucleophilic addition or substitution products. In this project, how the H2O2 or other oxidants or different additives (metal ions or other small molecules) to regulate the reaction characteristics of carbon-phosphine bonds will be practiced at first, so this reaction can effectively combine the properties of Wittig reagents, the oxidative ability and pollution-free by-products of H2O2 , it is obviously to take the advantages of the "1 +1> 2"combination regulation, and finally some compounds with unique structure or functions can be synthesized in one-pot reaction. The nucleophilicity of nitrogen or sulfur atom related reactions can be specifically explored on the carbon-phosphine bond in Wittig reagents. The results suggest that the combination of oxidants and metal ions or additives may affect the specific nucleophilicity of carbon-phosphine compounds or the specific reaction of coupling dimerization.

众所周知Wittig试剂（RCH=PPh3）可进攻羰基形成烯，但其氧化偶联二聚还极少报道过，且其他催化剂或助剂调控该特异性反应的系统研究则相对薄弱或缺乏深入的研究。本实验室近期工作表明，利用比较绿色的H2O2试剂可以氧化诱导Wittig试剂发生偶联二聚为烯烃而一步倍增其主体结构空间和分子量，或Wittig试剂可以进攻非羰基位点而形成特殊的加成或取代产物。本课题将首先研究H2O2等氧化剂及不同助剂（金属离子或其它小分子）是如何调控碳-膦键的反应特征的，以期有效组合利用H2O2自身无污染副产物的特点及Wittig试剂的特征调控，使其发挥“1+1>2” 的组合优势而一锅煮合成有独特结构及功能作用的化合物。可参照N原子S原子的亲核反应探索Wittig试剂碳-膦键的亲核反应及能力。相关结果为碳-膦化合物的独特亲核性或偶联二聚等特异性潜在的应用打下了基础

经典Wittig试剂的新应用扩展可以减少新原料的设计合成带来的难度或污染，同时还可以利用其碳负离子特征部分替换其他危险性大要求无水无氧的高活性C负离子试剂的应用。.. 本课题研究涉及到特殊Wittig试剂的合成如分子内多个C=P结构单元（2-4个）化合物的合成，同时还对其进行了氧化还原反应探索。还设计实施了Wittig试剂与亲核试剂如含硫等化合物的反应、不同炔类化合物合成及其与Ph3P/特殊多氟极性助剂组合作用下的位置选择性加成反应、柔性分子内双C=P结构单元分子的合成及其特殊的成环反应的调控。.. 相关研究可以得到独特的不同的位置选择性控制产物如末端烯烃或两端取代的烯烃、特殊含硫杂环化合物、多羰基体系、不同的五元或六元不饱和酯类化合物或吡喃酮类化合物。这大大扩展了Wittig试剂及其相关研究的应用。.