An Umpolung Approach to Alkene Carboamination: Palladium Catalyzed 1,2-Amino-Acylation, -Carboxylation, -Arylation, -Vinylation, and -Alkynylation,Journal of the American Chemical Society

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An Umpolung Approach to Alkene Carboamination: Palladium Catalyzed 1,2-Amino-Acylation, -Carboxylation, -Arylation, -Vinylation, and -Alkynylation
Journal of the American Chemical Society ( IF 14.4 ) Pub Date : 2015-05-28 , DOI: 10.1021/jacs.5b03732
Adele Faulkner ₁ , James S. Scott ₂ , John F. Bower ₁

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Conventional approaches to Pd-catalyzed alkene 1,2-carboamination rely upon the combination of a nucleophilic nitrogen-based component and an internal C-based or external oxidant. In this study, we outline an umpolung approach, which is triggered by oxidative initiation at an electrophilic N-based component and employs "standard" organometallic nucleophiles to introduce the new carbon-based fragment. Specifically, oxidative addition of a Pd(0)-catalyst into the N-O bond of O-pentafluorobenzoyl oxime esters generates imino-Pd(II) intermediates, which undergo 5-exo cyclization with sterically diverse alkenes. The resultant alkyl-Pd(II) intermediates are intercepted by organometallic nucleophiles or alcohols, under carbonylative or noncarbonylative conditions, to provide 1,2-carboamination products. This approach provides, for the first time, a unified strategy for achieving alkene 1,2-amino-acylation, -carboxylation, -arylation, -vinylation, and -alkynylation. For carbonylative processes, orchestrated protodecarboxylation of the pentafluorobenzoate leaving group underpins reaction efficiency. This process is likely a key feature in related Narasaka-Heck cyclizations and accounts for the efficacy of O-pentafluorobenzoyl oxime esters in aza-Heck reactions of this type.

中文翻译：

烯烃碳胺化的 Umpolung 方法：钯催化的 1,2-氨基-酰化、-羧化、-芳基化、-乙烯基化和-炔基化

Pd 催化的烯烃 1,2-碳化的传统方法依赖于亲核氮基组分和内部 C 基或外部氧化剂的组合。在这项研究中，我们概述了一种 umpolung 方法，该方法由亲电 N 基组件的氧化引发触发，并采用“标准”有机金属亲核试剂引入新的碳基片段。具体而言，将 Pd(0)-催化剂氧化加成到 O-五氟苯甲酰基肟酯的 NO 键中会生成亚氨基-Pd(II) 中间体，其与空间不同的烯烃进行 5-外环化。在羰基化或非羰基化条件下，生成的烷基-Pd(II) 中间体被有机金属亲核试剂或醇截获，以提供 1,2-碳化产物。这种方法提供，首次实现烯烃1,2-氨基-酰化、-羧化、-芳基化、-乙烯基化和-炔基化的统一策略。对于羰基化过程，五氟苯甲酸酯离去基团的协调原脱羧作用是反应效率的基础。该过程可能是相关 Narasaka-Heck 环化的关键特征，并解释了 O-五氟苯甲酰基肟酯在此类 aza-Heck 反应中的功效。

更新日期：2015-05-28

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