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Regioselective Copper-Catalyzed Oxidative Coupling of α-Alkylated Styrenes with Tertiary Alkyl Radicals
Cong Wang1, Rui-Hua Liu1, Ming-Qing Tian1
1Institute of Advanced Synthesis, School of Chemistry and Molecular Engineering, Jiangsu National Synergetic Innovation Center for Advanced Materials , Nanjing Tech University , Nanjing 211816 , China.
Abstract:
A radical-mediated oxidative cross-coupling of readily accessible α-alkylated styrenes with 1,3-dicarbonyl compounds utilizing a combination of Cu(OAc)2 and air as a catalytic system is described. Rather than requiring α-halocarbonyl compounds, this efficient approach enables direct installation of tertiary functionalized alkyl motifs to olefins with simple carbonyl derivatives. The novel protocol is characterized with high allylic selectivities via a competing β-H elimination. Both radical-clock and -trapping experiments provided clear-cut evidence for the intermediacy of an α-keto carbon-centered radical.
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