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Ferrocene-based Chiral Intramolecular Frustrated Lewis Pairs

Ferrocene-based Chiral Intramolecular Frustrated Lewis Pairs
基于二茂铁的手性分子内受阻路易斯对
批准号:
240618423
负责人:
Dr. Alain Charly Tagne Kuate
金额:
$0.0万
依托单位国家:
德国
项目类别:
Research Fellowships
财政年份:
2013
资助国家:
德国
项目状态:
已结题
起止时间:
2012-12-31 至 2016-12-31

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中文摘要
翻译
该研究项目涉及1,2-二茂铁基配体的适当设计,这些配体含有空间位阻的Lewis酸和体积较大的Lewis碱。这项工作的目标是合成具有平面手性和中心手性的Lewis对,并且能够:i)异解二氢裂解得到两性离子物种[LAH]-[LBH]+(LA=Lewis酸,Lb=Lewis碱),它可以进一步将两个氢原子以质子和氢化物的形式转移,使Lewis对被用作有机底物不对称氢化的催化剂和氢化物转移催化剂;ii)R3E-H(E=C,Si)键的活化允许Lewis对应用于例如催化不对称硅氢化和C-H硼化反应;(Iii)通过M-E回键作用实现过渡金属的双亲配位,这在催化交叉偶联反应中起着至关重要的作用;(Iii)小分子如CO2、N2O、P4、烯烃、二烯和炔烃的活化和固定,这将为探索新的反应途径提供令人兴奋的可能性。
英文摘要
The research project deals with the appropriate design of 1,2-ferrocenyl ligands bearing sterically encumbered Lewis acids and bulky Lewis bases. The goal of the work is to generate Lewis pairs featuring planar and central chirality and that are capable of: i) heterolytic dihydrogen cleavage to give the zwitterionic species [LAH]-[LBH]+ (LA = Lewis acid, LB = Lewis base), which can further transfer the two hydrogen atoms as a proton and an hydride, allowing the Lewis pair to be used as catalyst for the asymmetric hydrogenation of organic substrates and as hydride transfer catalyst; ii) activation of R3E-H (E = C, Si) bonds permitting application of the Lewis pair for example in catalytic asymmetric hydrosilylation and C-H borylation reactions;iii) behavior as ambiphilic ligand for the cooperative coordination of transition metals through M-E back bonding interactions that can plays a vital role in catalytic cross coupling reactions;(iii) activation and fixation of small molecules such as CO2, N2O, P4, alkenes, dienes and alkynes, which will provide thrilling possibilities to explore new reaction pathways.
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