Catalytic Conversion of Nitriles into Secondary- and Tertiary Amides
Catalytic Conversion of Nitriles into Secondary- and Tertiary Amides
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DOI：
10.1002/cctc.201200406
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发表时间：
2013-02-01
期刊：
影响因子：
4.5
通讯作者：
Williams, Jonathan M. J.
中科院分区：
文献类型：
--
作者：
Davulcu, Simge;Allen, C. Liana;Williams, Jonathan M. J.
酰胺官能团是生命和合成化学中最重要的官能团之一。改进的酰胺形成方法对于制药工业具有关键价值，由于其在生物学上重要的化合物中频繁出现，它们已被确定为药物化学中最受追捧的目标之一。[1]过渡金属催化胺与腈的亲核加成是形成仲酰胺和叔酰胺的一种有吸引力的合成方法，但受到的关注相对较少。[2]从原子效率的角度来看，使用过渡金属催化剂进行腈与胺的酰胺化是形成酰胺键的最理想的方法之一。近年来，人们投入了大量的精力来开发金属催化系统，用于从活化的羧酸衍生物（例如酰基氯）以外的起始材料合成酰胺，以避免使用化学计量偶合剂，而化学计量偶合剂在工业上现有的酰胺合成方法中经常需要[3]，因为化学计量偶合剂的使用会导致原子效率差并产生大量废物。 [4]最近对“绿色”化学和提高可持续性的重视凸显了催化过程的好处。[1b, 3] 已经建立了各种方法来催化形成酰胺键，无需化学计量活化剂的帮助。[3]这些方法包括一些优雅的过渡金属催化方法，包括均相和非均相，它们将炔烃、[5]醇、[6]酯、[7]醛、[8]甚至未活化的羧酸[9]与胺偶联。使用腈作为起始材料的过渡金属催化体系也已得到开发和深入探索，特别是在通过加水形成伯酰胺方面。腈的水合是合成伯酰胺最环保的方法之一。衍生自 PtII、[10] Rh、[11] Au、[12] Ru、[13] CuII、NiII 和 ZnII 的金属配合物均已被证明可以催化腈水合成伯酰胺。 [2a, 14] 尽管在形成伯酰胺的领域取得了进展，但从腈形成仲酰胺和叔酰胺的反应几乎没有先例。据我们所知，只有三个过渡金属催化方法的例子
The amide functionality is one of the most-important functional groups in life and in synthetic chemistry. Improved methods for the formation of amides are of key value for the pharmaceutical industry and they have been identified as one of the most-sought-after goals in pharmaceutical chemistry owing to their frequent occurrence in biologically important compounds.[1]The transition-metal-catalyzed nucleophilic addition of amines to nitriles is an attractive synthetic method for the formation of secondary-and tertiary amides but has received relatively little attention.[2] From the viewpoint of atom efficiency, the use of a transition-metal catalyst to effect the amidation of nitriles with amines represents one of the most-ideal methods for forming amide bonds. In recent years, considerable effort has been devoted to develop metal-catalyzed systems for the synthesis of amides from starting materials other than activated carboxylic-acid derivatives, such as acid chlorides, to avoid the use of stoichiometric coupling reagents, which are often required in the currently established methods for amide synthesis in industry,[3] because the use of stoichiometric coupling reagents leads to poor atom efficiency and the generation of large amounts of waste.[4] Recent emphasis on “greener” chemistry and improved sustainability has highlighted the benefits of catalytic processes.[1b, 3] Various methods have been established to form the amide bond catalytically without the aid of stoichiometric activating agents.[3] These methods include some elegant transitionmetal-catalyzed methodologies, both homogeneous and heterogeneous, which couple alkynes,[5] alcohols,[6] esters,[7] aldehydes,[8] and even unactivated carboxylic acids [9] with amines. Transition-metal-catalyzed systems that use nitriles as starting materials have also been developed and been well-explored, especially in the formation of primary amides by the addition of water. The hydration of nitriles is one of the mostenvironmentally friendly approaches to the synthesis of primary amides. Metal complexes that are derived from PtII,[10] Rh,[11] Au,[12] Ru,[13] CuII, NiII, and ZnII have all been shown to catalyze the hydration of nitriles into primary amides.[2a, 14] Despite advances in this area to form primary amides, reactions that form secondary-and tertiary amides from nitriles have very little precedent. To the best of our knowledge, there are only three examples of transition-metal-catalyzed methods for this