Direct Palladium(II)-Catalyzed Synthesis of Arylamidines from Aryltrifluoroborates

Sävmarker, Jonas; Rydfjord, Jonas; Gising, Johan; Odell, Luke R.; Larhed, Mats

doi:10.1021/ol300813c

Cited by 31 publications

(17 citation statements)

References 40 publications

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“…As a starting point for our investigation we conducted a solvent screen by using our previously developed catalytic system for aryl amidine synthesis from aryl trifluoroborates ([PdA C H T U N G T R E N N U N G (O 2 CCF 3 ) 2 ], 6-methyl-2,2'-bipyridyl (4) as the ligand and trifluoroacetic acid (TFA) as the proton donor). [45] 2,4,6-Trimethoxybenzoic acid (1 a) and N-cyanopiperidine (2 a) were chosen as model substrates and the catalyst and ligand loadings were set at 2 and 3 %, respectively. The reactions were then microwave (MW) heated [46] at 120 8C for 30 min using the appropriate solvent and 1 equivalent of TFA in sealed vessels.…”

Section: Resultsmentioning

confidence: 99%

“…Keywords: decarboxylation · density functional calculations · mass spectrometry · microwave chemistry · palladium through a palladium(II)-catalyzed 1,2-carbopalladation of cyanamides with aryltrifluoroborates (Scheme 1 b). [45] To further extend the utility of this direct amidine synthesis we decided to investigate the viability of carboxylic acids as the arylpalladium precursor. Herein, we present a fast and convenient protocol for the preparation of aryl amidines from aryl carboxylic acids and cyanamides (Scheme 1 c).…”

Section: Introductionmentioning

confidence: 99%

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Decarboxylative Palladium(II)‐Catalyzed Synthesis of Aryl Amidines from Aryl Carboxylic Acids: Development and Mechanistic Investigation

Rydfjord

Svensson

Trejos

et al. 2013

Chemistry A European J

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A fast and convenient synthesis of aryl amidines starting from carboxylic acids and cyanamides is reported. The reaction was achieved by palladium(II)-catalysis in a one-step microwave protocol using [Pd(O2CCF3)2], 6-methyl-2,2′-bipyridyl and trifluoroacetic acid (TFA) in N-methylpyrrolidinone (NMP), providing the corresponding aryl amidines in moderate to excellent yields. The protocol is very robust with regards to the cyanamide coupling partner but requires electron-rich ortho-substituted aryl carboxylic acids. Mechanistic insight was provided by a DFT investigation and direct ESI-MS studies of the reaction. The results of the DFT study correlated well with the experimental findings and, together with the ESI-MS study, support the suggested mechanism. Furthermore, a scale-out (scale-up) was performed with a non-resonant microwave continuous-flow system, achieving a maximum throughput of 11 mmol h−1 by using a glass reactor with an inner diameter of 3 mm at a flow rate of 1 mL min−1.

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Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Decarboxylative Palladium(II)‐Catalyzed Synthesis of Aryl Amidines from Aryl Carboxylic Acids: Development and Mechanistic Investigation

Rydfjord

Svensson

Trejos

et al. 2013

Chemistry A European J

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“…图式 17 N-酰基氰胺自由基串联反应合成四环稠合喹唑啉 Scheme 17 Radical cascade reaction of N-acyl cyanamides for the synthesis of tetracycle-fused quinazolines 几年后, 他们 [53] 除了应用于环脒类化合物的合成, 通过氰胺反应合成链状脒类化合物也已有相关报道. 2012 年, Larhed 课题组 [54] 通过钯催化芳基三氟硼酸钾 103 和氰胺 104 的…”

Section: 氰基化合物的合成unclassified

Progress on the Synthesis and Applications of Cyanamides

Li¹,

Li²,

Zhang³

et al. 2017

Chin. J. Org. Chem.

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Cyanamides are an important class of fine chemicals containing amino and cyano functionalities, which have been widely used for the synthesis of pharmaceuticals, agricultural chemicals, health products and materials, and attracted considerable attention from both organic synthetic chemists and medicinal chemists. Great advances in the synthesis and transformations of cyanamides were made, a diversity of synthetic methods and transformations of cyanamides were developed in the past two decades. In this paper, various synthetic methods and reactions of cyanamides are introduced comprehensively, their characteristics, rules, advantages and disadvantages are also summarized and discussed for the development of new synthetic methods and reactions of cyanamides.

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“…[3] Ag reatm anyi nhibitors of cathepsin contain the N-CN motif (Scheme 2). Furthermore,c yanamides also serve as versatileb uilding blocks in the construction of amidines, [5] ureas, [6] guanidines [7] and as eries of complexh eterocyclic structures (Scheme3). The N-acylcyanamide analogues such as compound 3 could inhibit the hepatitis Cv irus NS3 protease (Scheme 2).…”

Section: The Features Of Cyanamidesmentioning

confidence: 99%

The Construction of X–CN (X=N, S, O) Bonds

Teng

Cheng

2016

Adv Synth Catal

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Thec yano moiety is ac ommon and important functional group that exists in am yriado fm edicinal molecules and natural products.M oreover, nitriles serve as versatilep recursors that can readily be converted into diverse functional groups as well as the nitrogen-containing cyclic molecules.A s ar esult, cyanation has become as ignificant type of transformation in organic chemistry.H owever, in comparison with the well-developed C-cyanation, few works have been reported dealing with the N-, S-and O-cyanation processes.A part from the classical von Braun reaction, chemists have developed an umber of methods with various cyanating reagents to achieve such X-cyanations (X = N, S, O). In this review,r ecent advances( especially those after 2000) in the X-CN (X = N, S, O) bondf ormation are summarized with discussion andt he outlooksa re also listed.1I ntroduction 2F ormation of the N-CN Bond 2.Scheme 23. Iodine(III)-promted cleavage of C-S bonds leading to thiocyanates.Scheme 24. Tr aditional methods for constructing the O-CN bond.

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Direct Palladium(II)-Catalyzed Synthesis of Arylamidines from Aryltrifluoroborates

Cited by 31 publications

References 40 publications

Decarboxylative Palladium(II)‐Catalyzed Synthesis of Aryl Amidines from Aryl Carboxylic Acids: Development and Mechanistic Investigation

Decarboxylative Palladium(II)‐Catalyzed Synthesis of Aryl Amidines from Aryl Carboxylic Acids: Development and Mechanistic Investigation

Progress on the Synthesis and Applications of Cyanamides

The Construction of X–CN (X=N, S, O) Bonds

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