Chemoselective Ru-Catalyzed Oxidative Lactamization <i>vs</i> Hydroamination of Alkynylamines: Insights from Experimental and Density Functional Theory Studies

Álvarez‐Constantino, Andrés M.; Álvarez‐Pérez, Andrea; Varela, Jesús A.; Sciortino, Giuseppe; Ujaque, Gregori; Saá, Carlos

doi:10.1021/acs.joc.2c02770

Cited by 4 publications

(2 citation statements)

References 51 publications

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“…HRMS (ESI + ): m/z (M + H) + calcd for C 9 H 8 ClNO: 182.0367; found: 182.0358. 1,3,4,5-Tetrahydro-2H-1-benzazepin-2-one (2t) 38 Purified by silica gel (300-400 mesh) column chromatography (PE/EtOAc 5:1); yield: 12.6 mg (26%); white solid; mp 135-136 °C.…”

Section: P Wang S Zhangmentioning

confidence: 99%

Synthesis of Oxindoles via SmI2-Promoted Reduction of 2-Nitrophenylacetic Acids

Zhang,

Wang

2023

Synthesis

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Section: P Wang S Zhangmentioning

confidence: 99%

Synthesis of Oxindoles via SmI2-Promoted Reduction of 2-Nitrophenylacetic Acids

Zhang,

Wang

2023

Synthesis

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“…For C–C π-systems in which a C–N bond is installed, the method of activation, which serves as the basis for chemical selectivity, is of fundamental importance . As the method of activation cannot always be inferred from basic reaction principles, detailed experimental and computational studies are required to identify the exact mechanistic pathways . Furthermore, the predicted transformation is assumed to involve an intermediate that differs from the generic intermediate .…”

Section: Introductionmentioning

confidence: 99%

Acetate Assistance in Regioselective Hydroamination of Allenamides: A Combined Experimental and Density Functional Theory Study

Pradhan,

Farah,

Sagar

et al. 2024

J. Org. Chem.

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A key factor in the development of selective nucleophilic addition to allenamides is controlling the reactivity of electrophilic intermediates, which is generally achieved using an electrophilic activator via conjugated iminium intermediates. In this combined experimental and computational study, we show that a general and highly chemoselective hydroamination of allenamides can be accomplished using a combination of 1,1,1,3,3,3-hexafluoro-2-propanol (HFIP) and NaOAc. Experimental mechanistic studies revealed that HFIP mediates proton transfer to activate the allenamide, while the acetate additive significantly contributes to N-selective interception. This strategy enables a general hydroamination of allenamides without the use of metals. We demonstrated that various functionalized 1,3-diamines could be readily synthesized and diversified into value-added structural motifs. Detailed mechanistic investigations using the density functional theory revealed the role of NaOAc in the formation of reactive electrophilic intermediates, which ultimately governed the selective formation of 1,3-diamine products. Critically, calculations of the potential energy surface around the proton-transfer transition state revealed that two different reactive electrophilic intermediates were formed when NaOAc was added.

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Ring Expansion Reactions through Intramolecular Transamidation

Kalinin,

Sapegin

2023

Eur J Org Chem

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Synthetic methodologies based on cycle expansion reactions have proven to be highly effective in delivering valuable medium‐sized cycles and macrocycles. A primary method of ring expansion relies on intramolecular transamidation reactions. These reactions typically employ N‐aminoalkyl and N‐aminoacyl derivatives of lactams and their analogues as starting materials, yielding a diverse spectrum of unique nitrogen‐containing heterocycles. This Review aims to provide a comprehensive analysis of the research outcomes related to intramolecular transamidation reactions that lead to cycle expansion. This will offer the reader a perspective on the potential applications of such reactions in generating novel and intriguing types of heterocyclic systems.

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Chemoselective Ru-Catalyzed Oxidative Lactamization vs Hydroamination of Alkynylamines: Insights from Experimental and Density Functional Theory Studies

Cited by 4 publications

References 51 publications

Synthesis of Oxindoles via SmI2-Promoted Reduction of 2-Nitrophenylacetic Acids

Synthesis of Oxindoles via SmI2-Promoted Reduction of 2-Nitrophenylacetic Acids

Acetate Assistance in Regioselective Hydroamination of Allenamides: A Combined Experimental and Density Functional Theory Study

Ring Expansion Reactions through Intramolecular Transamidation

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