Chambers Kristian J, Sanghong Patthadon, Carter Martos Daniel, Casoni Giorgia, Mykura Rory C, Prasad Hari Durga, Noble Adam, Aggarwal Varinder K
School of Chemistry, University of Bristol, Cantock's Close, BS8 1TS, Bristol, UK.
Angew Chem Int Ed Engl. 2023 Dec 11;62(50):e202312054. doi: 10.1002/anie.202312054. Epub 2023 Nov 9.
Enones are widely utilized linchpin functional groups in chemical synthesis and molecular biology. We herein report the direct conversion of boronic esters into enones using commercially available methoxyallene as a three-carbon building block. Following boronate complex formation by reaction of the boronic ester with lithiated-methoxyallene, protonation triggers a stereospecific 1,2-migration before oxidation generates the enone. The protocol shows broad substrate scope and complete enantiospecificity is observed with chiral migrating groups. In addition, various electrophiles could be used to induce 1,2-migration and give a much broader range of α-functionalized enones. Finally, the methodology was applied to a 14-step synthesis of the enone-containing polyketide 10-deoxymethynolide.
烯酮是化学合成和分子生物学中广泛使用的关键官能团。我们在此报告了使用市售的甲氧基丙二烯作为三碳结构单元将硼酸酯直接转化为烯酮。硼酸酯与锂化甲氧基丙二烯反应形成硼酸酯配合物后，质子化引发立体特异性的1,2-迁移，然后氧化生成烯酮。该方法具有广泛的底物范围，并且在手性迁移基团存在下观察到完全的对映体特异性。此外，各种亲电试剂可用于诱导1,2-迁移，并得到范围更广的α-官能化烯酮。最后，该方法应用于含烯酮的聚酮化合物10-脱氧甲炔诺内酯的14步合成。
