Amidation of Alcohols with Nitriles under Solvent-free Conditions Using Molecular Iodine as a Catalyst

Kasashima, Yoshio; Uzawa, Atsushi; Hashimoto, Kimio; Yokoyama, Yû; Mino, Takashi; Sakamoto, Masami; Fujita, Tsutomu

doi:10.5650/jos.59.607

Cited by 15 publications

(8 citation statements)

References 20 publications

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“…[24] Using a recently developed iodine-catalyzed Ritter reaction performed at a 120°C, (−)-borneol led to an amide product whose relative stereochemistry was clearly demonstrated by x-ray crystal structure analysis to be the inversion product. [25] Ritter reactions of bornyl and isobornyl chloride in the presence of SbCl 5 in acetonitrile have been shown to give the same exo -amide product [26] suggesting a common carbocation intermediate and a preference for exo -attack. [27] In the case of isoborneol (entry 4), the present method gave only the stereoretentive amide ( exo -product) product 15 albeit in low yield (21%).…”

Section: Resultsmentioning

confidence: 99%

Stereoretentive Copper(II)‐Catalyzed Ritter Reactions of Secondary Cycloalkanols

Al‐Huniti

Lepore

2013

Adv Synth Catal

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A Ritter-like coupling reaction of cyclic alcohols and both aryl and alkyl nitriles to form amides catalyzed by copper (II) triflate is described. These reactions proceed in good yields under mild and often solvent-free conditions. With 2- and 3-substituted cycloalkanols, amide products are formed with near complete retention of configuration. This is likely due to fast nucleophilic capture of a non-planar carbocations (hyperconjomers) stabilized by ring hyperconjugation. A critical aspect of this novel catalytic cycle is the in situ activation of the alcohol substrates by thionyl chloride to form chlorosulfites.

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Section: Resultsmentioning

confidence: 99%

Stereoretentive Copper(II)‐Catalyzed Ritter Reactions of Secondary Cycloalkanols

Al‐Huniti

Lepore

2013

Adv Synth Catal

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“…As a result, two amide compounds having different stereostructures are produced, as shown in Scheme 3. We previously reported that the amidation of (-) -borneol with benzonitrile using iodine as the catalyst gave the racemic amide compound 8) . The same results were obtained when using both the 3 0 0 a (120 ) a The amide compound was not obtained, but (7) was obtained in 90% yield.…”

Section: Resultsmentioning

confidence: 99%

“…In addition, iodine was known to be an efficient catalyst in solvent-free reactions [4][5][6][7] . We previously reported that the amidation of alcohols with nitriles proceeded smoothly under solvent-free conditions using iodine as the catalyst 8) . In this study, we investigated the amidation of esters with nitriles.…”

Section: Introductionmentioning

confidence: 99%

Amide Synthesis from Esters with Nitriles under Solvent-free Conditions Using Molecular Iodine as a Catalyst

et al. 2012

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and ZnCl 2 /SiO 2 12). These are strong acids or heavy metal compounds, which are very expensive and/or toxic. In addition, solvent-free reactions are important in green chemistry. Accordingly, we investigated the amidation of esters Abstract: The reaction of esters with nitriles, using iodine as a catalyst under solvent-free conditions, was investigated. For example, 1-phenylethyl acetate reacted with benzonitrile in the presence of iodine to afford the amide, N-(1-phenylethyl)benzamide. Addition of water was effective in promoting amidation. The most suitable conditions were investigated, and determined as follows: temperature = 80℃, molar ratio of nitrile:alcohol:iodine:water = 1:3:0.2:1.0, and reaction time = 18 h. The amidation reactivity depended on the stability of the cationic intermediate formed from the ester. Only the reaction of 2-phenylpropan-2-yl acetate with benzonitrile gave no amide compound; rather, the cyclic compound, 1,1,3-trimethyl-3-phenyl-2,3-dihydro-1H-indene was obtained in 90% yield. The reaction of (-)-bornyl acetate with benzonitrile produced the racemic amide compound, (±)-exo-N-isobornylbenzamide, in 82% yield.

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“…The product was washed with cooled diethyl ether (2 Â 3 mL).rac-3: 61% (precipitated from the reaction mixture and washed by Et 2 O); colorless crystals; mp: 113°C, lit 24. mp 100-101°C, 1 H NMR (CDCl 3 ): 1.54 (3H, d, J = 7.2 Hz, CH 3 ), 3.31 (2H, s, CH 2 ), 5.10 (1H, dq, J = 7.2 Hz and J = 7.3 Hz, CH), 6.53 (1H, br, NH), 7.28-7.40 (5H, m, ArH); 13 C NMR (CDCl 3 ): 21.7 (CH 3 ), 26.1 (CH 2 ), 50.2 (CH), 114.9 (CN), 126.3 (2xCH), 128.0 (CH), 129.1 (2xCH), 142.2 (C) 160.3 (C@O); IR (KBr): 3279, 3068, 2975, 2921, 2258, 1648, 1554, 669.…”

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confidence: 99%

Chemoenzymatic route to Tyrphostins involving lipase-catalyzed kinetic resolution of 1-phenylethanamine with alkyl cyanoacetates as novel acylating agents

Csuka

Boros

Őrfi

et al. 2015

Tetrahedron: Asymmetry

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Amidation of Alcohols with Nitriles under Solvent-free Conditions Using Molecular Iodine as a Catalyst

Cited by 15 publications

References 20 publications

Stereoretentive Copper(II)‐Catalyzed Ritter Reactions of Secondary Cycloalkanols

Stereoretentive Copper(II)‐Catalyzed Ritter Reactions of Secondary Cycloalkanols

Amide Synthesis from Esters with Nitriles under Solvent-free Conditions Using Molecular Iodine as a Catalyst

Chemoenzymatic route to Tyrphostins involving lipase-catalyzed kinetic resolution of 1-phenylethanamine with alkyl cyanoacetates as novel acylating agents

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