Here we report a palladium-catalysed difunctionalisation of unsaturated C−C bonds with acid chlorides. Formally, the C−COCl bond of an acid chloride is cleaved and added, with complete atom economy, across either strained alkenes or a tethered alkyne to generate new acid chlorides. The transformation does not require exogenous carbon monoxide, operates under mild conditions, shows a good functional group tolerance, and gives the isolated products with excellent stereoselectivity. The intermolecular reaction tolerates both aryl- and alkenyl-substituted acid chlorides and is successful when carboxylic acids are transformed to the acid chloride in situ. The reaction also shows an example of temperature-dependent stereodivergence which, together with plausible mechanistic pathways, is investigated by DFT calculations. Moreover, we show that benzofurans can be formed in an intramolecular variant of the reaction. Finally, derivatisation of the products from the intermolecular reaction provides a highly stereoselective approach for the synthesis of tetrasubstituted cyclopentanes.

中文翻译：

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通过 C-COCl 键裂解催化不饱和烃的碳氯羰基化**

在这里，我们报告了钯催化的不饱和 C-C 键与酰氯的双官能化。正式地，酰氯的 C-COCl 键被裂解并添加，具有完全的原子经济性，跨越紧张的烯烃或系链的炔烃，以生成新的酰氯。该转化不需要外源一氧化碳，在温和条件下操作，显示出良好的官能团耐受性，并提供具有优异立体选择性的分离产物。分子间反应可耐受芳基和烯基取代的酰氯，当羧酸原位转化为酰氯时，该反应是成功的。该反应还显示了温度依赖性立体发散的一个例子，它与合理的机械途径一起通过 DFT 计算进行了研究。而且，我们表明苯并呋喃可以在反应的分子内变体中形成。最后，分子间反应产物的衍生化为合成四取代环戊烷提供了一种高度立体选择性的方法。