Regioselective radical alpha-borylation of alpha,beta-unsaturated carbonyl compounds for direct synthesis of alpha-borylcarbonyl molecules
Regioselective radical alpha-borylation of alpha,beta-unsaturated carbonyl compounds for direct synthesis of alpha-borylcarbonyl molecules
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α,β-不饱和羰基化合物的区域选择性自由基α-硼基化用于直接合成α-硼基羰基分子
DOI：
10.1038/s41467-019-09825-3
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发表时间：
2019
影响因子：
16.6
通讯作者：
Wang Yi-Feng
中科院分区：
文献类型：
--
作者：
Ren Shi-Chao;Zhang Feng-Lian;Xu Ai-Qing;Yang Yinuo;Zheng Min;Zhou Xiaoguo;Fu Yao;Wang Yi-Feng
有机硼化合物在合成化学中具有很高的价值。特别是，α-硼基羰基化合物由于硼基和羰基部分的富有成效的化学而显示出多方面的合成应用。然而，这些分子的合成仍然是繁琐和耗时的。本文报道了一种直接、实用的合成α-硼基羰基分子的方法，该方法基于α，β-不饱和羰基化合物的区域选择性自由基α-硼基化反应。该反应具有特殊的α-区域选择性和高的官能团相容性。还展示了新的α-硼基化产物的进一步合成应用。密度泛函理论和动力学研究表明，β-芳基-α，β-不饱和羰基化合物的α-区域选择性是由热力学上更有利的自由基α-加成步骤决定的，而β-烷基-α，β-不饱和羰基化合物的α-加成产物的形成是由热力学上更有利的氢原子转移步骤驱动的.由于α，β-不饱和羰基化合物的来源丰富多样，该方法在合成有价值的α-硼基羰基化合物方面具有多样性和经济性的优势。
Organoboron compounds are highly valuable in synthetic chemistry. In particular, α-borylcarbonyl compounds have shown versatile synthetic applications, owing to fruitful chemistries of both the boryl and carbonyl moieties. However, the synthesis of these molecules still remains tedious and time-consuming. Here we report a straightforward and practical route to synthesizeα-borylcarbonyl molecules based on a regioselective radicalα-borylation ofα,β-unsaturated carbonyl compounds. The reaction features unusualα-regioselectivity and high functional-group compatibility. Further synthetic applications of newα-borylated products were also demonstrated. DFT and kinetic studies implicated that theα-regioselectivity ofβ-aryl-α,β-unsaturated carbonyl compounds was determined by the thermodynamically more favorable radicalα-addition step, whereas the formation ofα-addition products fromβ-alkyl-α,β-unsaturated carbonyl compounds was driven by an energetically favored hydrogen atom transfer step. Given thatα,β-unsaturated carbonyl compounds can be easily obtained in abundance and variety, this method enjoys great advantages in diverse and economical synthesis of valuableα-borylcarbonyl molecules.