Functionalization and Hydrogenation of Carbon Chains Derived from CO**
Functionalization and Hydrogenation of Carbon Chains Derived from CO**
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CO 衍生的碳链的官能化和氢化**
DOI：
10.1002/ange.202202241
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发表时间：
2022
影响因子：
--
通讯作者：
Batuecas M
中科院分区：
文献类型：
--
作者：
Batuecas M
报道了联合收割机H2、CO与有机亲电试剂（醛、酮、异腈）反应生成氢化C3和C4碳链的选择性反应。这些反应通过由[W（CO）6]和铝（I）还原剂介导的CO同系化进行，然后通过链端的官能化和氢化进行。动力学（速率，KIE）和DFT计算的组合已被用来深入了解一个关键的步骤，其中涉及氢化的一个双卡宾中间体。这些发现扩展了联合收割机H2和CO的极小范围的系统，以制造对链长和功能完全控制的定义明确的产品。
Selective reactions that combine H2, CO and organic electrophiles (aldehyde, ketones, isocyanide) to form hydrogenated C3and C4carbon chains are reported. These reactions proceed by CO homologation mediated by [W(CO)6] and an aluminum(I) reductant, followed by functionalization and hydrogenation of the chain ends. A combination of kinetics (rates, KIEs) and DFT calculations has been used to gain insight into a key step which involves hydrogenation of a metallocarbene intermediate. These findings expand the extremely small scope of systems that combine H2and CO to make well‐defined products with complete control over chain length and functionality.