727733-92-8Relevant articles and documents
Late-Stage N-Me Selective Arylation of Trialkylamines Enabled by Ni/Photoredox Dual Catalysis
Shen, Yangyang,Rovis, Tomislav
supporting information, p. 16364 - 16369 (2021/10/21)
The diversity and wide availability of trialkylamines render them ideal sources for rapid construction of complex amine architectures. Herein, we report that a nickel/photoredox dual catalysis strategy affects site-selective α-arylation of various trialkylamines. Our catalytic system shows exclusive N-Me selectivity with a wide range of trialkylamines under mild conditions, even in the context of late-stage arylation of pharmaceutical compounds bearing this common structural motif. Mechanistic studies indicate the unconventional behavior of Ni catalyst upon intercepting the α-amino radicals, in which only the primary α-amino radical undergoes a successful cross-coupling process.
Direct Catalytic Decarboxylative Amination of Aryl Acetic Acids
Kong, Duanyang,Moon, Patrick J.,Bsharat, Odey,Lundgren, Rylan J.
supporting information, p. 1313 - 1319 (2019/12/15)
The decarboxylative coupling of a carboxylic acid with an amine nucleophile provides an alternative to the substitution of traditional organohalide coupling partners. Benzoic and alkynyl acids may be directly aminated by oxidative catalysis. In contrast, methods for intermolecular alkyl carboxylic acid to amine conversion, including amidate rearrangements and photoredox-promoted approaches, require stoichiometric activation of the acid unit to generate isocyanate or radical intermediates. Reported here is a process for the direct chemoselective decarboxylative amination of electron-poor arylacetates by oxidative Cu catalysis. The reaction proceeds at (or near) room temperature, uses native carboxylic acid starting materials, and is compatible with protic, electrophilic, and other potentially complicating functionality. Mechanistic studies support a pathway in which ionic decarboxylation of the acid generates a benzylic nucleophile which is aminated in a Chan–Evans–Lam-type process.
Photoredox-catalyzed Direct Reductive Amination of Aldehydes without an External Hydrogen/Hydride Source
Alam, Rauful,Molander, Gary A.
supporting information, p. 2680 - 2684 (2018/05/22)
The direct reductive amination of aromatic aldehydes has been realized using a photocatalyst under visible light irradiation. The single electron oxidation of an in situ formed aminal species generates the putative α-amino radical that eventually delivers the reductive amination product. This method is operationally simple, highly selective, and functional group tolerant, which allows the direct synthesis of benzylic amines by a unique mechanistic pathway.
