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Catalytic cleavage and functionalization of bulky and inert Csp3–Csp3 bonds via a relayed proton-coupled electron transfer strategy
Cell Reports Physical Science ( IF 7.9 ) Pub Date : 2022-02-16 , DOI: 10.1016/j.xcrp.2022.100763
Ke Liao 1 , Fengjin Wu 2 , Jiean Chen 3 , Yong Huang 2
Affiliation  

Catalytic cleavage and functionalization of unstrained carbon–carbon bonds represent a formidable challenge for synthetic chemistry. Despite tremendous advances in transition-metal catalysis and photoredox radical chemistry, methods for the cleavage of sterically crowded inert Csp3–Csp3 bonds remain underdeveloped. Here we describe the direct, photoredox cleavage of hindered Csp3–Csp3 bonds of alcohols under neutral conditions. A relayed proton-coupled electron transfer (PCET) strategy is employed that overcame the previous requirement of a Brønsted base. Heavily branched alcohols with a high oxidation potential (Eox½ > +2 V versus saturated calomel electrode) are cleaved and functionalized with remarkable efficiency and versatility. A simple, non-substituted phenyl group can promote a relayed PCET process to deliver primary, secondary, and tertiary alkyl radicals under neutral conditions.



中文翻译:

通过中继质子耦合电子转移策略催化裂解和功能化庞大和惰性的 Csp3-Csp3 键

无应变碳-碳键的催化裂解和功能化对合成化学来说是一项艰巨的挑战。尽管在过渡金属催化和光氧化还原自由基化学方面取得了巨大进步,但裂解空间拥挤惰性 C sp3 -C sp3键的方法仍然不发达。在这里,我们描述了在中性条件下醇的受阻 C sp3 -C sp3键的直接光氧化还原裂解。采用中继质子耦合电子转移 (PCET) 策略,克服了之前对 Brønsted 碱基的要求。具有高氧化电位的重支化醇 ( E ox½> +2 V vs 饱和甘汞电极)被切割和功能化,具有显着的效率和多功能性。一个简单的、未取代的苯基可以促进中继的 PCET 过程,以在中性条件下传递伯、仲和叔烷基自由基。

更新日期:2022-02-16
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