Alkanes, the main constituents of petroleum, are attractive feedstocks for producing value-added chemicals. Linear aldehydes and amines are two of the most important building blocks in the chemical industry. To date, there have been no effective methods for directly converting n-alkanes to linear aldehydes and linear amines. Here, we report a molecular dual-catalyst system for production of linear aldehydes via regioselective carbonylation of n-alkanes. The system is comprised of a pincer iridium catalyst for transfer-dehydrogenation of the alkane using t-butylethylene or ethylene as a hydrogen acceptor working sequentially with a rhodium catalyst for olefin isomerization-hydroformylation with syngas. The system exhibits high regioselectivity for linear aldehydes and gives high catalytic turnover numbers when using ethylene as the acceptor. In addition, the direct conversion of light alkanes, n-pentane and n-hexane, to siloxy-terminated alkyl aldehydes through a sequence of Ir/Fe-catalyzed alkane silylation and Ir/Rh-catalyzed alkane carbonylation, is described. Finally, the Ir/Rh dual-catalyst strategy has been successfully applied to regioselective alkane aminomethylation to form linear alkyl amines.

中文翻译：

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烷烃热催化转化为直链醛和直链胺

烷烃是石油的主要成分，是生产增值化学品的有吸引力的原料。线性醛和胺是化学工业中最重要的两种结构单元。迄今为止，还没有将正烷烃直接转化为直链醛和直链胺的有效方法。在这里，我们报告了一种通过正构烷烃的区域选择性羰基化生产线性醛的分子双催化剂系统。该系统由使用叔丁基乙烯或乙烯作为氢受体的用于烷烃转移-脱氢的钳状铱催化剂与用于烯烃异构化-加氢甲酰化与合成气的铑催化剂依次工作组成。该系统对线性醛表现出高区域选择性，并在使用乙烯作为受体时提供高催化周转数。此外，还描述了轻质烷烃、正戊烷和正己烷通过 Ir/Fe 催化的烷烃甲硅烷基化和 Ir/Rh 催化的烷烃羰基化的序列直接转化为甲硅烷氧基封端的烷基醛。最后，Ir/Rh 双催化剂策略已成功应用于区域选择性烷烃氨甲基化以形成线性烷基胺。