Carbenes are highly enabling reactive intermediates that facilitate a diverse range of otherwise inaccessible chemistry, including small-ring formation and insertion into strong σ bonds. To access such valuable reactivity, reagents with high entropic or enthalpic driving forces are often used, including explosive (diazo) or unstable ( gem -dihalo) compounds. Here, we report that common aldehydes are readily converted (via stable α-acyloxy halide intermediates) to electronically diverse (donor or neutral) carbenes to facilitate >10 reaction classes. This strategy enables safe reactivity of nonstabilized carbenes from alkyl, aryl, and formyl aldehydes via zinc carbenoids. Earth-abundant metal salts [iron(II) chloride (FeCl 2 ), cobalt(II) chloride (CoCl 2 ), copper(I) chloride (CuCl)] are effective catalysts for these chemoselective carbene additions to σ and π bonds.

中文翻译：

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烷基醛和芳基醛的卡宾反应性

卡宾是高度活跃的反应中间体，可促进各种其他方式无法实现的化学反应，包括小环形成和插入强σ键。为了获得如此有价值的反应性，通常使用具有高熵或热函驱动力的试剂，包括爆炸性（重氮）或不稳定的（宝石-二卤）化合物。在这里，我们报告常见的醛很容易转化（通过稳定的α-酰氧基卤化物中间体）为电子多样化（供体或中性）卡宾，以促进> 10个反应类别。该策略使得来自烷基醛、芳基醛和甲酰醛的不稳定卡宾能够通过锌类卡宾进行安全反应。地球上丰富的金属盐[氯化铁(II) (FeCl2), 氯化钴(II) (CoCl2）、氯化铜（I）（CuCl）]是这些化学选择性卡宾加成到 σ 和 π 键的有效催化剂。