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

沮丧的刘易斯对化学 在一篇开创性的《科学》文章中，我们报道了在不使用过渡金属的情况下氢的异解裂解。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”(FLP)化学的一般领域产生了世界范围的活动。我们已经扩展了Flp在化学计量化学以及催化中的应用，反复发现非金属体系能够提供新的和有趣的转化方法的令人震惊的例子。在这项建议中，我们着重于三个主要领域的新发展： (I)新型供硼氟磷化合物的开发和探索及其用途 (2)氟氯烃在化学计量和催化反应中的应用以及 (3)基于磷的Lewis酸的发展、它们的反应性和这种体系的含义。 在(I)中，我们探索了新的合成路线，包括CO还原、点击化学，并探索了由此产生的反应活性。此外，还开发了含硼阳离子和以配体为辅基的有趣的金属基氟磷灰石。 在(II)中，我们建议将FLP-芳香族氢化扩展到有机合成中，而“受挫自由基对”(FRP)被用来影响C-H键的活化。FLP-氢胺化催化的最新进展将扩展到炔烃和烯烃的氢磷化或氢硫醇化，CO2的催化还原将精制为以H2为还原剂。 在(Iii)中，我们利用我们最新的《科学》文章开发了基于膦的Lewis酸，阐述了这些体系在Lewis酸催化中的应用，因为这些sigma*-受体有望具有官能团容忍性，为广泛应用铺平了道路。我们还设想在FLP化学中使用基于P的Lewis酸。此外，我们还将探索磷杂环的氢化反应，这将为直接使用氢气的有机底物的氢化提供一种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.