乙烯基
化学
光化学
增强碳-碳
吡啶
碳纤维
激进的
药物化学
有机化学
二苯甲酮
材料科学
复合数
复合材料
作者
Junhyuk Jo,S. Kim,Seonyoung Park,Seonyul Kim,Sunggi Lee,Jun‐Ho Choi,Won‐jin Chung
标识
DOI:10.1021/acs.joc.4c00946
摘要
Ketyl radicals are synthetically versatile reactive species, but their applications have been hampered by harsh generation conditions employing highly reducing metals. Recently, the pyridine-boryl radical received wide attention as a promising organic reductant because of its mildness as well as convenience in handling. While probing the utility of the pyridine-boryl radical, our group observed facile pinacol coupling reactivity that had not been known at that time. This serendipitous finding was successfully rendered into a practical synthesis of tetraaryl-1,2-diols in up to 99% yield within 1 h. Subsequently, upon examinations of various reaction manifolds, a diastereoselective ketyl-olefin cyclization was accomplished to produce cycloalkanols such as trans-2-alkyl-1-indanols. Compared to the previous methods, the stereocontrolling ability was considerably enhanced by taking advantage of the structurally modifiable boryl group that would be present near the bond-forming site. In this full account, our synthetic efforts with the O-boryl ketyl radicals are disclosed in detail, covering the discovery, optimization, scope expansion, and mechanistic analysis, including density functional theory (DFT) calculations.
科研通智能强力驱动
Strongly Powered by AbleSci AI