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P=C-N Systems: Potential of benzazaphospholes for transition metal complexes with non-classical P hybrid ligands, for bulky P-substituted heterocyclic phosphane ligands, complexes and catalysts and for benzazaphospholium salts as precursors of P,N-heteroc

P=C-N 系统：苯并磷杂化物与非经典 P 杂化配体的过渡金属配合物、大体积 P-取代杂环磷烷配体、配合物和催化剂以及苯并磷鎓盐作为 P,N-杂环化合物前体的潜力

基本信息

批准号：
228481794
负责人：
Professor Dr. Joachim Heinicke
金额：
--
依托单位：
Institut für Biochemie
依托单位国家：
德国
项目类别：
Research Grants
财政年份：
2012
资助国家：
德国
起止时间：
2011-12-31 至 2014-12-31
项目状态：
已结题

来源：
https://gepris.dfg.de/gepris/projekt/228481794?language=en
关键词：
P=C Systems Potential benzazaphospholes transition

项目摘要

Reactivity studies of aromatically stabilized P=C-N heterocycles, specially of various N- and C-substituted 1,3-benzazaphospholes and related coplanar tetracyclic P=C-N-heterocycles, shall be carried out with the following objectives:- Synthesis and structural characterization of complexes of mono- and bidentate heterocyclic P=C-N-ligands and (P=C-N),P- or (P=C-N),N hybrid ligands with mono- and divalent transition metal ions as novel type of complexes for potential use in transition metal catalysis.- Development of a new synthesis strategy to mono- and bidentate bulky and electronrich P-tert-butyl substituted P,N heterocyclic phosphane ligands by controlled addition at the P=C-N structure group with emphasis to enantioselective P=C addition, induced by an asymmetric N-substituent. This shall lead to new asymmetric P,N ligands which might be useful for transition metal catalyzed enantioselective organic transformations. - Conversion of benzazaphospholes into N,P-dineopentyl-benzazaphospholium salts, exploration of their properties and synthesis potential for the access to novel P,N-heterocyclic carbene complexes. By isolation and structural characterization of such a complex we want to gain knowledge on the influence of the fixation of the two heteroatoms in a five-memebred ring on the properties of these carbenes. So far only acyclic representatives are known. Carbene complexes of various types have found extremely manifold applications in catalytic reactions.

芳香稳定的P=C-N杂环，特别是各种N-和C-取代的1，3-苯并氮杂磷杂环戊烯和相关的共面四环P=C-N杂环的反应性研究应按照以下目标进行：合成和结构表征单齿和双齿杂环P=C-N-配体和（P=C-N），P-或（P=C-N），N杂合配体与一价和二价过渡金属离子的配合物，作为潜在用于过渡金属催化的新型配合物。通过在P=C-N结构基团上的控制加成，重点是由不对称N-取代基诱导的对映选择性P=C加成，发展了一种新的合成策略来合成单齿和双齿的大体积和富电子的P-叔丁基取代的P，N杂环膦配体。这将导致新的不对称的P，N配体，可能是有用的过渡金属催化的不对称有机转化。- 将苯并氮杂磷杂茂转化为N，P-二新戊基-苯并氮杂磷杂茂盐，探索其性质和合成潜力，以获得新型的P，N-杂环卡宾配合物。通过对这种配合物的分离和结构表征，我们希望了解五元环中两个杂原子的固定对这些卡宾性质的影响。到目前为止，只有非循环的代表是已知的。各种类型的碳烯络合物在催化反应中已发现极其多方面的应用。