新型磷亚胺类分子内受阻路易斯酸碱对的合成及研究

In recent years, the research on the chemistry of frustrated Lewis pairs has received remarkable and wide attention, especially for the small molecules activation and catalytic hydrogenation. Nevertheless, the current limitations of existing frustrated Lewis pairs(FLPs) system are largely dependent on highly fluorinated, but strongly Lewis acidic boranes, which are expensive、synthetically hindered and time-consuming. Exploring novel frustrated Lewis pairs systems and new reactions and applications in organic synthesis are critical to the development of FLP chemistry. The project aims to design a novel, efficient and highly functional group tolerated intramolecular N/B system employing the "reverse Lewis acid-base pair" strategy. It is hoped that by combining the design and synthesis of bulky and strong basic phosphazine compounds with weak Lewis acid boron reagent would result in novel intramolecular FLPs, increasing the basicity of Lewis base can reduce the cost of strong Lewis acid and dependence on highly fluorinated borane compounds. The "reverse" strategy provides a new approach to the design of FLP-based systems, which consists strong basic phosphazine with simple and readily available, low-cost, weak acidic boron compounds. The development of such system is intended to provide theoretical and methodological support for the development of highly efficient non-metallic activation systems and for the activation of non-metallic organic small molecules and the application of new organocatalysts.

近年来，针对新型非金属催化体系受限路易斯酸碱对（FLPs）化学的研究备受国内外广泛关注，尤其是对小分子的活化及催化氢化反应。但是，目前受限路易斯酸碱对体系大多局限在成本昂贵、合成条件苛刻的大位阻多氟取代芳基强路易斯酸硼试剂。探索新型受阻路易斯酸碱对体系及在有机合成中的新反应对FLP化学的发展至关重要。本项目拟借助“反转法”策略来设计合成新型、高效、高官能团耐受性的分子内N/B体系。希望通过设计合成具有受阻强碱类磷亚胺化合物与弱路易斯酸硼试剂构建分子内“受阻路易斯酸碱对”，提高路易斯碱的强度可以减少对强路易斯酸高成本、多氟类硼试剂的依赖性。这种‘‘反转的’’途径为设计基于强碱磷亚胺、简单易得、低成本弱酸硼试剂受阻路易斯酸碱催化体系提供了新的方法，进一步拓展了FLP的体系。开发该类体系旨在为发展高效的非金属活化体系，并为非金属有机小分子活化及在新型有机催化中的应用研究提供理论和方法学支持。

近年来，针对新型催化体系受限路易斯酸碱对（FLPs）化学的研究备受国内外广泛关注，尤其是将其应用小分子活化到聚合反应制备功能高分子材料是目前该领域的研究热点。设计合成新型的路易斯酸和路易斯碱来构建新型的受阻路易斯酸碱对体系对FLP化学的发展至关重要。.本项设计合成双核铝试剂作为路易斯酸，与商品化的膦试剂构建路易斯酸碱对，并将其应用到极性单体甲基丙烯酸甲酯和丙烯酸丁酯的可控聚合领域，聚合结果表明双核铝路易斯比单核铝路易斯酸具有更好的聚合可控性，通过检测活性中间体，提出了新的聚合机理。为室温下实现上述两种单体的可控聚合提供了新思路。此外，还设计合成了新型的碱吡啶烯和硫脲铵盐作为路易斯碱，可分别用于小分子活化和生物质单体丁内酯的开环聚合中。