We have developed a reductive carbonylation method by which unactivated alkyl iodides can be hydroxymethylated to provide one‐carbon‐extended alcohol products under Cu‐catalyzed conditions. The method is tolerant of alkyl β‐hydrogen atoms, is robust towards a wide variety of functional groups, and was applied to primary, secondary, and tertiary alkyl iodide substrates. Mechanistic experiments indicate that the transformation proceeds by atom‐transfer carbonylation (ATC) of the alkyl iodide followed in tandem by two CuH‐mediated reductions in rapid succession. This radical mechanism renders the Cu‐catalyzed system complementary to precious‐metal‐catalyzed reductive carbonylation reactions.

中文翻译：

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铜催化未活化烷基碘与CO的羟甲基化反应，以提供单碳扩展醇

我们已经开发了一种还原性羰基化方法，通过该方法可以将未活化的烷基碘进行羟甲基化，从而在Cu催化的条件下提供碳扩展的醇产物。该方法可耐受烷基β-氢原子，对多种官能团均具有较强的耐受性，并已应用于伯，仲和叔烷基碘的底物。机理实验表明，转化是通过烷基碘的原子转移羰基化（ATC）进行的，随后是两次CuH介导的快速连续还原。这种自由基机理使铜催化体系与贵金属催化的还原羰基化反应互补。