设计并研究廉价FLPs参与的CO2活化反应

The reversible addition of FLPs to CO2 was widely focused in recent years. While, the chemistry of FLPs with CO2 is not yet developed. Most of FLPs are relied on expensive tris(pentafluorophenyl)borane and toxic phosphine reagents. Meanwhile, only limited works on FLPs catalysed CO2 reduction reactions were reported. With these problems, we proposed to design a series of intramolecular FLPs with low costs and less toxic reagents. We will study the effects of CO2 addition on different type of Lewis acids/bases and different structure of intramolecular FLPs. Based on these intramolecular FLPs, we would like to achieve FLPs catalysed the reaction of weak organometallic reagents with CO2 to afford various carboxylic acids. It will be a valuable protocol for synthesis of carboxylic acids with CO2 activation.

近年来，FLPs可逆性加成CO2气体的独特活性被广泛关注。然而，目前为止FLPs对CO2活化的研究还存在很大局限性，大多的FLPs依赖于昂贵的多氟硼试剂和剧毒的有机磷试剂；且仅有零星的FLPs催化的CO2还原反应被报道。针对这些问题，申请人计划设计优化一系列廉价的、低毒性的分子内FLPs，研究其对CO2的活化能力，探究Lewis酸碱的类型、结构对CO2加成的影响；在此基础上，并进一步深入探索FLPs催化弱金属亲核试剂的CO2加成反应，合成各类羧酸化合物，为非金属催化的CO2活化的提供新途径。

CO2由于其廉价易得、低毒性、且是可再生资源，因此被用来作为C1合成子在有机合成中广泛应用。然而由于其惰性很难被活化，因此发展廉价且高效的催化剂活化CO2是目前研究的热点之一。本项目发展了廉价的吡啶胺-硼烷的FLP催化体系，可以高效活化CO2，实现1、对有机胺的选择性还原生成甲基化或者甲酰化产物；2、对醛/酮和胺串联还原得到叔丁胺类化合物；于此同时也实现了3、芳基锌试剂的直接羧酸化反应；4、Co催化的脱硼质子化反应；5、Cu催化的对二苯肼的脱氢氧化反应；6、B(C6F5)3催化的烯胺还原反应等。