Deconstructive Cyanomethylation Enabled by Radical Cross-Coupling through Multiple C−C Bond and C−H Bond Cleavage,Advanced Synthesis & Catalysis

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Deconstructive Cyanomethylation Enabled by Radical Cross-Coupling through Multiple C−C Bond and C−H Bond Cleavage
Advanced Synthesis & Catalysis ( IF 4.4 ) Pub Date : 2023-03-16 , DOI: 10.1002/adsc.202300183
Changzhen Yin ₁ , Wei Liu ₁ , Qiang Wu ₁ , Miao Wang ₁ , Peng Hu ₂

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Being in its infancy, radical cross-coupling is highly efficient for C−C bond construction, though suffers from selectivity problems and limited reaction types. New methodologies to realize radical cross-coupling selectively are highly desired. Herein, an iron catalyzed deconstructive cyanomethylation of unstrained cyclic and linear alcohols with acetonitrile has been developed through radical cross-coupling. The unprecedented method enables a ring-opening functionalization of cyclohexanols to produce α-cyanomethyl ketones. Notably, the highly challenging reaction involves twice C−C single bond cleavage through β-scission of alkoxyl radical intermediates, and twice C(sp³)−H bond transformation via hydrogen atom transfer (HAT) procedures, resulting in two carbon radical species that realize a radical cross-coupling process to form a new C(sp³)−C(sp³) bond selectively. α-arylketo and α-aryl substituted tertiary alcohols can also be applied as substrates, leading to terminal cyano-functionalized linear products, with ketone as the leaving fragment. Mechanistically, a new procedure to generate alkoxyl radical with chlorine radical through the in-situ formed intermediate cycloalkyl hypochlorite was suggested.

中文翻译：

通过多个 C−C 键和 C−H 键断裂的自由基交叉偶联实现解构性氰甲基化

处于起步阶段的自由基交叉偶联对 C-C 键的构建非常有效，但存在选择性问题和有限的反应类型。非常需要有选择地实现激进交叉耦合的新方法。在此，通过自由基交叉偶联开发了一种铁催化的无应变环状和直链醇与乙腈的解构氰甲基化反应。这种前所未有的方法使环己醇的开环功能化能够产生 α-氰甲基酮。值得注意的是，这个极具挑战性的反应涉及通过烷氧基自由基中间体的 β- 断裂进行两次 C-C 单键断裂，以及两次 C( sp ³ )-H 键转换氢原子转移 (HAT) 过程，导致两个碳自由基物种实现自由基交叉偶联过程，选择性地形成新的 C( sp ³ )−C( sp ³ ) 键。α-芳基酮和 α-芳基取代的叔醇也可以用作底物，产生末端氰基官能化的线性产物，其中酮作为离去片段。在机理上，提出了一种通过原位形成的中间体次氯酸环烷基酯与氯自由基生成烷氧基自由基的新方法。

更新日期：2023-03-16

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