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Study on Pyridine-Boryl Radical-Promoted, Ketyl Radical-Mediated Carbon–Carbon Bond-Forming Reactions
The Journal of Organic Chemistry ( IF 3.3 ) Pub Date : 2024-06-11 , DOI: 10.1021/acs.joc.4c00946 Junhyuk Jo 1 , Somi Kim 1 , Seonyoung Park 1 , Seonyul Kim 1 , Sunggi Lee 2 , Jun-Ho Choi 1 , Won-Jin Chung 1
The Journal of Organic Chemistry ( IF 3.3 ) Pub Date : 2024-06-11 , DOI: 10.1021/acs.joc.4c00946 Junhyuk Jo 1 , Somi Kim 1 , Seonyoung Park 1 , Seonyul Kim 1 , Sunggi Lee 2 , Jun-Ho Choi 1 , Won-Jin Chung 1
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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.
中文翻译：
吡啶-硼基自由基促进、羰基自由基介导的碳-碳键形成反应的研究
羰基自由基是合成上通用的活性物质，但其应用受到使用高还原性金属的恶劣生成条件的阻碍。近年来，吡啶硼基自由基作为一种有前景的有机还原剂因其温和且易于处理而受到广泛关注。在探索吡啶-硼基自由基的用途时，我们的小组观察到了当时未知的频哪醇偶联反应性。这一偶然发现成功地转化为四芳基-1,2-二醇的实际合成，1 小时内收率高达 99%。随后，在对各种反应歧管进行检查后，完成了非对映选择性羰基-烯烃环化以产生环烷醇，例如反式-2-烷基-1-茚满醇。与以前的方法相比，通过利用成键位点附近存在的结构可修饰的硼基，立体控制能力得到了显着增强。在这份完整的报告中，详细披露了我们对O-硼基羰基自由基的合成工作，涵盖发现、优化、范围扩展和机理分析，包括密度泛函理论 (DFT) 计算。
更新日期：2024-06-11
中文翻译：
吡啶-硼基自由基促进、羰基自由基介导的碳-碳键形成反应的研究
羰基自由基是合成上通用的活性物质，但其应用受到使用高还原性金属的恶劣生成条件的阻碍。近年来，吡啶硼基自由基作为一种有前景的有机还原剂因其温和且易于处理而受到广泛关注。在探索吡啶-硼基自由基的用途时，我们的小组观察到了当时未知的频哪醇偶联反应性。这一偶然发现成功地转化为四芳基-1,2-二醇的实际合成，1 小时内收率高达 99%。随后，在对各种反应歧管进行检查后，完成了非对映选择性羰基-烯烃环化以产生环烷醇，例如反式-2-烷基-1-茚满醇。与以前的方法相比，通过利用成键位点附近存在的结构可修饰的硼基，立体控制能力得到了显着增强。在这份完整的报告中，详细披露了我们对O-硼基羰基自由基的合成工作，涵盖发现、优化、范围扩展和机理分析，包括密度泛函理论 (DFT) 计算。
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