A protocol of amide-to-amine transformation that is convenient, mild, and easy to perform is a long-sought goal from the viewpoint of catalysis. Herein, we have utilized easily accessible W(CO)₄(NCMe)₂ as a precatalyst for the deoxygenative reduction of 1°, 2° and 3° amides under mild conditions. Mechanism studies unraveled that the in situ generated W₄-cluster is potentially a vital species in activating C═O of amides by providing the H-bonding network during the catalytic cycle. Significantly, this tactic offers a complementary pattern to conventional metal-catalyzed amide deoxygenative reactions with activation of the C═O bond via direct coordination with amide.

中文翻译：

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通过原位生成的钨簇作为氢键供体实现 1°、2° 和 3° 酰胺的脱氧还原


从催化的角度来看，方便、温和且易于执行的酰胺-胺转化方案是一个长期寻求的目标。在此，我们利用易于接近的 W（CO）₄（NCMe）₂ 作为预催化剂，在温和条件下对 1°、2° 和 3° 酰胺进行脱氧还原。机理研究揭示了原位生成的 W₄ 簇可能是通过在催化循环中提供 H 键网络来激活酰胺 C═O 的重要物质。值得注意的是，这种策略为传统的金属催化酰胺脱氧反应提供了一种互补模式，通过与酰胺的直接配位激活 C═O 键。