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

“受挫的路易斯对”：无金属合成和催化

• 批准号: RGPIN-2014-05300
• 负责人: Stephan, Douglas
• 金额: $ 11.29万
• 依托单位: University of Toronto
• 依托单位国家: 加拿大
• 项目类别: Discovery Grants Program - Individual
• 财政年份: 2018
• 资助国家: 加拿大
• 起止时间: 2018-01-01 至 2019-12-31
• 项目状态: 已结题
• 来源: https://www.nserc-crsng.gc.ca/ase-oro/Details-Detailles_eng.asp?id=665920
• 关键词: Frustrated; Lewis; Pairs; Metal; Free

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.

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H2的异裂裂解。这一发现为无金属氢化催化打开了大门，并在“受挫折的刘易斯对”（FLP）化学领域产生了世界范围的活动。我们已经扩展了FLP在化学计量化学和催化中的应用，反复发现非金属系统提供新的有趣的转化方法的能力的令人震惊的例子。在本提案中，我们将重点关注三个主要领域的新发展：*（i）新型硼供体FLP及其实用性的开发和探索 *（ii）FLP在化学计量和催化反应性中的应用 *（iii）磷基刘易斯酸的开发，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，以获得基于硼的FLP，并探索了所得的反应性。 Borenium阳离子和有趣的金属为基础的FLP中的配体是辅助的也被开发。** 在（ii）中，我们提出了将FLP-芳香族氢化扩展到有机合成中的应用，而“受抑自由基对”（FRPs）用于实现C-H键活化。 FLP-氢胺化催化的最新发展将扩展到炔和烯烃的氢膦化或氢硫醇化，并且将改进CO2的催化还原以使用H2作为还原剂。在（iii）中，我们利用我们最近的科学文章开发了基于磷的刘易斯酸，以详细说明这种系统在刘易斯酸催化中的应用，因为这些σ * 受体预计是官能团耐受的，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的刘易斯酸。此外，我们还将探测磷杂环的氢化，从而为直接使用H2的有机底物的氢化提供前所未有的有机催化途径。