"Frustrated Lewis Pairs": Metal-Free Synthesis and Catalysis

在一篇影响深远的科学文章中，我们报道了H2的异裂解而不使用过渡金属。这一发现为无金属氢化催化打开了大门，并在“受挫刘易斯对”（FLPs）化学的一般领域产生了全球性的活动。我们扩展了FLPs在化学计量化学以及催化方面的应用，不断发现非金属体系能够提供新的和有趣的方式来实现转化的令人震惊的例子。在本提案中，我们将重点关注新发展的三个主要领域：*(i)新型硼供体FLPs的开发和探索及其用途*(ii) FLPs在化学计量学和催化反应性中的应用*(iii)磷基路易斯酸的开发，其反应性和此类系统的含义。*在(i)中，我们探索了新的合成路线，包括co还原，点击化学，以硼基FLPs，并探索了所得的反应性。硼离子和有趣的金属基FLPs，其中配体是辅助的也发展。**在（ii）中，我们提出将flp -芳香族氢化扩展到有机合成中，而“受挫自由基对”（FRPs）则用于影响C-H键的激活。flp -氢胺化催化的最新发展将扩展到炔烃和烯烃的氢膦化或氢硫化，并将CO2的催化还原精制为以H2为还原剂。**在（iii）中，我们利用我们最近发表在《科学》杂志上的文章，开发了基于磷的路易斯酸，以详细设计用于路易斯酸催化的系统，因为这些sigma*受体有望具有官能团耐受性，为广泛应用铺平了道路。我们还设想在FLP化学中使用p基路易斯酸。此外，我们还将探索磷杂环的加氢，为直接利用H2进行有机底物加氢提供前所未有的有机催化途径。

Frustrated Lewis Pairs Chemistry *In a seminal Science article, we reported the heterolytic cleavage of H2 without using a transition metal. That finding opened the door to metal-free hydrogenation catalysis and spawning world-wide activity in the general area of "frustrated Lewis pairs" (FLPs) chemistry. We have extended the applications of FLPs in stoichiometric chemistry, as well as in catalysis, repeatedly finding shocking examples of the ability of non-metal systems to provide new and interesting ways to effect transformation. In this proposal, we are focused on three major areas for new developments: *(i) the development and exploration of new types of Boron-donor FLPs and their utility *(ii) the applications of FLPs in stoichiometric and catalytic reactivity and *(iii) the development of phosphorus-based Lewis acids, their reactivity and the implication of such systems. *In (i) we probed new synthetic route including CO-reduction, click-chemistry, to boron-based FLPs and explore the resulting reactivity. Borenium cations and interesting metal-based FLPs in which the ligand is ancillary are also developed. **In (ii) we propose an expansion of FLP-aromatic hydrogenation to applications in organic synthesis, while "frustrated radical pairs" (FRPs) are employed to effect C-H bond activations. The recent development of FLP-hydroamination catalysis will be expanded to hydrophosphination or hydrothiolation of alkynes and olefins and the catalytic reductions of CO2 will be refined to employ H2 as the reductant.**In (iii) we exploit our most recent Science article to develop phosphonium-based Lewis acids to elaborate such systems for applications in Lewis acid catalysis as these sigma*-acceptors are expected to be functional group tolerant, paving the way to widespread applications. We also envision the use of P-based Lewis acids in FLP chemistry. Moreover, we will also probe hydrogenation of phosphorus heterocycles raising the promise of an unprecedented organo-catalytic route to the hydrogenation of organic substrates employing H2 directly.