Regioselective radical α-borylation of α,β-unsaturated carbonyl compounds for direct synthesis of α-borylcarbonyl molecules
| Autor: | Yao Fu, Min Zheng, Yinuo Yang, Xiaoguo Zhou, Feng-Lian Zhang, Shi-Chao Ren, Ai-Qing Xu, Yi-Feng Wang |
|---|---|
| Jazyk: | angličtina |
| Rok vydání: | 2019 |
| Předmět: |
0301 basic medicine
Reactive precursors Reaction mechanisms Science General Physics and Astronomy Synthetic chemistry methodology 02 engineering and technology Chemical synthesis Borylation General Biochemistry Genetics and Molecular Biology Article 03 medical and health sciences chemistry.chemical_compound Molecule lcsh:Science Multidisciplinary Chemistry Synthon Regioselectivity General Chemistry Hydrogen atom 021001 nanoscience & nanotechnology Combinatorial chemistry 030104 developmental biology Functional group lcsh:Q Organic synthesis 0210 nano-technology |
| Zdroj: | Nature Communications, Vol 10, Iss 1, Pp 1-10 (2019) Nature Communications |
| ISSN: | 2041-1723 |
| Popis: | 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 synthesize α-borylcarbonyl molecules based on a regioselective radical α-borylation of α,β-unsaturated carbonyl compounds. The reaction features unusual α-regioselectivity and high functional-group compatibility. Further synthetic applications of new α-borylated products were also demonstrated. DFT and kinetic studies implicated that the α-regioselectivity of β-aryl-α,β-unsaturated carbonyl compounds was determined by the thermodynamically more favorable radical α-addition step, whereas the formation of α-addition products from β-alkyl-α,β-unsaturated carbonyl compounds was driven by an energetically favored hydrogen atom transfer step. Given that α,β-unsaturated carbonyl compounds can be easily obtained in abundance and variety, this method enjoys great advantages in diverse and economical synthesis of valuable α-borylcarbonyl molecules. α-Borylcarbonyl compounds are versatile synthons in organic synthesis, however their preparation is often tedious. Here, the authors report a regioselective radical α-borylation of α,β-unsaturated carbonyl compounds to afford α-borylcarbonyl molecules with high selectivity and functional group compatibility. |
| Databáze: | OpenAIRE |
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