DABCO‐Promoted Decarboxylative Acylation: Synthesis of α‐Keto and α,β‐Unsaturated Amides or Esters

Zhang, Junrong; Liao, Yulin; Deng, Jiyong; Tang, Zi-Liang; Xu, Yuan-Lin; Xu, Lijin; Tang, Ri‐Yuan

doi:10.1002/ajoc.201600591

Cited by 15 publications

(5 citation statements)

References 42 publications

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“…In principle, the 1,2-dicarbonyl entity could be fully recovered, but the ethyl benzoylformate used in this reaction was hydrolyzed under the strong basic conditions. Several other 1,2-dicarbonyl reagents [62][63][64] were subsequently examined to circumvent this process. Unfortunately, none of the examined reagents could promote the preceding N-H insertion reaction (see the SI for the screening of 1,2-dicarbonyl compounds).…”

Section: Resultsmentioning

confidence: 99%

Kukhtin–Ramirez-Reaction-Inspired Deprotection of Sulfamidates for the Synthesis of Amino Sugars

et al. 2022

Molecules

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Herein, we present a mild strategy for deprotecting cyclic sulfamidates via the Kukhtin–Ramirez reaction to access amino sugars. The method features the removal of the sulfonic group of cyclic sulfamidates, which occurs through an N-H insertion reaction that implicates the Kukhtin–Ramirez adducts, followed by a base-promoted reductive N-S bond cleavage. The mild reaction conditions of the protocol enable the formation of amino alcohols including analogs that bear multiple functional groups.

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Section: Resultsmentioning

confidence: 99%

Kukhtin–Ramirez-Reaction-Inspired Deprotection of Sulfamidates for the Synthesis of Amino Sugars

et al. 2022

Molecules

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“…Besides, BMIZnCl 3 was recyclable. In 2017, the Tang group elaborated a DABCO‐promoted synthesis of α,β ‐unsaturated amides or esters. Cinnamic acids reacted with carbamic chlorides to produce acid anhydrides, which underwent the decarboxylative recombination process to provide corresponding products.…”

Section: Acids As Nucleophiliesmentioning

confidence: 99%

Recent Advances of Cinnamic Acids in Organic Synthesis

et al. 2020

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The great success of cinnamic acids was rooted in their multiple functional groups. Herein, reactions triggered by the radical addition, electrophilic addition, Michael addition and reactions of acids were thoroughly discussed and summarized. Multi-component reactions, rearrange-ments, stereoselective synthesis, coupling, additions will be depicted in detail. This review focused on advances of cinnamic acids in the last decade (2010)(2011)(2012)(2013)(2014)(2015)(2016)(2017)(2018)(2019)(2020). We hope this review will be good for a better understanding of these reagents and future research. * , [7,8] acyl [9] and ketonic [10] radicals were reported. Toluene, [8a-c,9] boron reagents, [8d] aldehydes, [8e] acids, [9b,c] amides, [9d,12e-f] ketones, [10a-b] ethers, [11a-c] alcohols, [12a] epoxides, [12b] nitriles [12a] were able to function as radical precursors.Mao and co-workers [4] reported the decarboxylative methylation of cinnamic acids. The DTBP was employed not only as the oxidant, but also as the methyl source.C vinyl À CF 3 compounds (like Panomifene, and Cyhalothrin) were useful in medicinal chemistry. [5b] Hence, numerous efforts have been devoted to the preparation of these compounds. In this decade, several applications of air-stable Togni's reagent [5a-c,6a] or NaSO 2 CF 3 [5d-f,6b] for the direct C vinyl À CF 3 construction from cinnamic acids have been reported. These radical addition and decarboxylative methods usually required a metal-catalyst (Ir, [5a] Cu [5c,e,6b] ) (Scheme 3)Hu and co-workers [6a] presented a protocol for the construction of C sp2 À CF 2 SO 2 R bonds with a Togni-type reagent. The [a] L.Scheme 1. Classification by mechanism Scheme 2. Radical cascade.

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“…Due to the large relevance of propiolamides, several synthetic strategies have been developed recently for their preparation including non-catalytic methodologies [20][21][22][23][24][25][26][27] that, although can be practical, are not efficient from the viewpoint of atom economy. Regarding catalytic methods, protocols employing amide-based compounds, [28][29][30][31][32] isocyanates [33] or isocyanides [34][35] have been also explored in the presence of homogeneous catalytic systems.…”

Section: Introductionmentioning

confidence: 99%

A General and Highly Versatile Heterogeneous Pd‐Catalyzed Oxidative Aminocarbonylation of Alkynes with Aromatic and Aliphatic Amines

Arango‐Daza,

Cabrero‐Antonino,

Adam

2024

ChemSusChem

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An efficient heterogeneous catalytic system for the oxidative aminocarbonylation of alkynes and amines in the presence of CO/O2 to afford substituted propiolamides has been developed. The active nanocatalyst, [Pd/Mg3Al‐LDH]‐300(D), is composed by Pd nanoaggregates (2‐3 nm average particle size) stabilized over a partially dehydrated [Mg3Al‐LDH] matrix. The methodology has resulted widely applicable, being the first catalytic system, either homogeneous or heterogeneous, able to activate not only aliphatic amines but also poorly‐nucleophilic aromatic amines. In fact, >60 substituted propiolamides have been synthesized in good to excellent isolated yields through this methodology, being 27 novel compounds. An important characterization effort (XRD, 27Al MAS NMR, TGA, TPD‐CO2, BET area, XPS, HAADF‐HRSTEM and HRTEM) and optimization of the synthesis conditions of the optimal catalyst has been performed. This study, together with a series of kinetic and mechanistic essays, indicates that the optimal catalyst is composed by Pd(0) species stabilized in a partially dehydrated/dehydroxylated LDH material with a Mg/Al molar ratio of 3 and a small crystallite size. All the experimental data indicates that the in situ formation of [PdI2] active species in the material surface together with the presence of a matrix with the optimal acid/base properties are key aspects of this process.

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DABCO‐Promoted Decarboxylative Acylation: Synthesis of α‐Keto and α,β‐Unsaturated Amides or Esters

Cited by 15 publications

References 42 publications

Kukhtin–Ramirez-Reaction-Inspired Deprotection of Sulfamidates for the Synthesis of Amino Sugars

Kukhtin–Ramirez-Reaction-Inspired Deprotection of Sulfamidates for the Synthesis of Amino Sugars

Recent Advances of Cinnamic Acids in Organic Synthesis

A General and Highly Versatile Heterogeneous Pd‐Catalyzed Oxidative Aminocarbonylation of Alkynes with Aromatic and Aliphatic Amines

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