RUI-Synthesis and applications of cyclic boronic half acids

通过这个RUI奖，化学合成项目支持巴特勒大学的LuAnne McNulty教授的研究，研究烯基环硼半酯的制备和反应。烯基环硼半酯是由同丙烯醇与烯基硼酸酯交换，然后合环复合反应制备的。烯基环硼半酯是与芳基卤化物和-晕- α、-不饱和亲电试剂进行Suzuki-Miyaura交叉偶联反应的合适底物。Suzuki-Miyaura提供的产品能够进行分子内oxa-Michael反应生成二氢吡喃。通过对偶联反应中使用的碱-晕- α、-不饱和亲电试剂进行修饰，研究单锅串联Suzuki-Miyaura/Michael反应的优化。提出的工作努力提供一种替代方法来制备二氢吡喃，常见的天然产物亚结构单位。此外，这项工作可以允许人们通过在前体环硼酸烯基上修饰取代基来设置相同的二氢吡喃的多个立体异构体。该项目在教育方面的广泛影响包括培养本科生。PI将继续她在合成研究中指导女性的悠久历史。参与本项目的本科生将获得现代合成化学的宝贵经验，包括有机硼和过渡金属介导的化学，并将有机会在地区和国家会议上展示他们的工作。

With this RUI Award, the Chemical Synthesis Program is supporting the research of Professor LuAnne McNulty of Butler University to study the preparation and reactions of alkenyl cyclic boronic half esters. Alkenyl cyclic boronic half esters are readily prepared by transesterification of homoallylic alcohols with alkenylboronic acids, followed by ring closing metathesis. Alkenyl cyclic boronic half esters are suitable substrates for Suzuki-Miyaura cross-coupling reactions with aryl halides and beta-halo-alpha,beta-unsaturated electrophiles. The Suzuki-Miyaura affords products that are capable of undergoing an intramolecular oxa-Michael reaction to generate dihydropyrans. The optimization of a single pot tandem Suzuki-Miyaura/Michael reaction will be studied through the modification of the base beta-halo-alpha,beta-unsaturated electrophiles used in the coupling reaction. The proposed work strives to provide an alternate method to the preparation of dihydropyrans, common natural product substructural units. In addition, the work could allow one to set multiple stereoisomers of the same dihydropyran by modification of substituents on the precursor alkenyl cyclic boronate. The educational broader impacts of this project involve training undergraduate students. The PI will continue her strong history of mentoring women in synthetic research. Undergraduate students that participate in this project will gain valuable experience in modern synthetic chemistry, including organo-boron and transition metal-mediated chemistry, and will have opportunities to present their work at regional and national meetings.