Direct oxidative conversion of alkyl halides into nitriles with molecular iodine and 1,3-diiodo-5,5-dimethylhydantoin in aq ammonia

Iida, Shinpei; Ohmura, Ryosuke; Togo, Hideo

doi:10.1016/j.tet.2009.05.001

Cited by 54 publications

(12 citation statements)

References 27 publications

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“…The residue was purified with flash column chromatography (SiO 2 , n-hexane-EtOAc=4 : 4,5,6,7-Tetraf luoro-2-(4-methoxybenzyloxy)-3-(2,2,2-trifluoroethoxy)-3-trifluoromethylisoindolin-1-one (33) According to the procedure described for the preparation of ether 32 from alcohol 31 in which 2,2,2-trifluoroenthanol was used as the alcohol instead, alcohol 31 (1.00 g, 2.35 mmol) was converted into ether 33 (0.593 g, 50%). 35) b, 36) g, 37) h, 38) j, 39) and k 40) were prepared following the reported procedures. General Procedure for Benzoate from Alcohol (Procedure C) 3-(4-Methoxyphenyl)propyl Benzoate (36c) To a solution of 3-(4-methoxyphenyl)-1-propanol 42c (1.66 g, 10.0 mmol) in CH 2 Cl 2 (20 mL), BzCl (1.39 mL, 12.0 mol) and pyridine (1.93 mL, 24.0 mmmol) were added at 0°C.…”

Section: General Procedures For Hydrogenolysis Of Benzyl Ether (Procedmentioning

confidence: 99%

Enhanced Structural Variety of Nonplanar <i>N</i>-Oxyl Radical Catalysts and Their Application to the Aerobic Oxidation of Benzylic C–H Bonds

Kadoh

Oisaki

Kanai

2016

CHEMICAL & PHARMACEUTICAL BULLETIN

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The design and synthesis of structurally variable, nonplanar N-oxyl radical catalysts and their application to the aerobic oxidation, etherification, and acetoamidation of benzylic C-H bonds are described. The catalytic oxidation of C-H bonds represents a powerful tool to synthesize oxygenated functional molecules from simple hydrocarbons in a straightforward way. Electron-deficient N-oxyl radical catalysts, such as phthalimidoyl N-oxyl (PINO) radical, generated from N-hydroxyphthalimide (1), have attracted much attention because of their applications in the oxidation of C-H bonds with high bond dissociation energy (BDE). However, a few sites in 1 are available for structural modifications and improvements of the catalytic performance. By replacing one carbonyl group in 1 with a trifluoromethyl (CF 3 )-substituted sp 3 -carbon, we generated an additional tunable site and a nonplanar backbone, while retaining the desirable electronwithdrawing properties and increasing the lipophilicity with respect to 1. We synthesized a variety of Nhydroxy pre catalysts containing such a CF 3 moiety, and investigated their utility in the aerobic oxidation of benzylic C-H bonds. Precatalysts with electron-withdrawing substituents, such as trifluoroethoxy and the acetophenone moieties, afforded higher yields than a corresponding methoxy-substituted analogue. The introduction of substituents at the aromatic ring was also effective, as evident from the performance of 7-CF 3 and 4,5,6,7-tetrafluoro precatalysts. Especially the combination of trifluoroethoxy-and 4,5,6,7-tetrafluoro substitution afforded a superior performance. These catalyst systems exhibited high functional group tolerance during the aerobic oxidation of C-H bonds, and benzylic etherification and Ritter-type reactions could be carried out at room temperature when a selected precatalyst and N-bromosuccinimide (NBS) were used.

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Section: General Procedures For Hydrogenolysis Of Benzyl Ether (Procedmentioning

confidence: 99%

Enhanced Structural Variety of Nonplanar <i>N</i>-Oxyl Radical Catalysts and Their Application to the Aerobic Oxidation of Benzylic C–H Bonds

Kadoh

Oisaki

Kanai

2016

CHEMICAL & PHARMACEUTICAL BULLETIN

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“…It has been for years that benzyl cyanides and azides are known for various synthetic applications . The former is addressed as one of the most important precursors for the synthesis of amides, carboxylic acids, ketones, amines and esters .…”

Section: Introductionmentioning

confidence: 99%

“…Owing to the growing significance of biologically active nitrogenous molecules, there is an emerging need for efficient synthetic methods to prepare such mentioned compounds. Among the various methods in providing these substantial chemicals in organic chemistry, nucleophilic substitution of aryl halides with inorganic sodium cyanide and azide has been survayed as one of the most typical and easiest methodologies.…”

Section: Introductionmentioning

confidence: 99%

Design and synthesis of a magnetic hierarchical porous organic polymer: A new platform in heterogeneous phase‐transfer catalysis

Mouradzadegun

Ganjali

Mostafavi

2018

Applied Organom Chemis

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Recyclable phase transfer catalysts containing magnetic nanoparticles (MNPs) have been known as a major trend towards sustainable catalysts. In this study, a novel class of magnetic porous polymer on the basis of calix[4]resorcinarene was synthesized starting from silica-coated Fe 3 O 4 core-shell nanoparticles. This compound was found as an efficient phase transfer catalyst to the conversion of benzyl halides into benzyl azides and cyanides in good yields. The catalyst could be used at least for five consecutive cycles without appreciable loss in the catalytic activity.

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“…using NH 4 HCO 3 /(Bu 4 N) 2 25 MnO 2 /NH 3 /MgSO 4 / THF-i-PrOH (for benzylic and cinnamic alcohols), 25 I 2 /aq NH 3 , 26 and DIH/aq NH 3 , 22 and KI/I 2 /TBHP. 27 Recently, the direct oxidative conversion of alkyl halides into nitriles with molecular iodine and 1,3-diiodo-5,5-dimethylhydantoin in aqueous ammonia was reported by Togo and et al 28 Trichloroisocyanuric acid [1,3,5-trichloro-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione or TCCA] is a stable, homogeneous, neutral, nonvolatile, inexpensive, safe, commercially available reagent (used primarily as a disinfectant and deodorant) that has been used as efficient catalyst, reagent, and oxidant in organic synthesis. [29][30][31][32][33][34] Recently, we reported the direct, efficient, practical, and less toxic oxidative conversion of primary alcohols and amines into the corresponding nitriles using poly(N,N¢-dichloro-N-ethylbenzene-1,3-disulfonamide) (PCBS) and N,N,N¢,N¢-tetrachlorobenzene-1,3-disulfonamide (TCBDA) in aqueous ammonia.…”

mentioning

confidence: 99%

Direct Oxidative Conversion of Alcohols, Amines, Aldehydes, and Benzyl Halides into the Corresponding Nitriles with Trichloroisocyanuric Acid in Aqueous Ammonia

Veisi¹

2010

Synthesis

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A new and efficient procedure for the one-pot conversion of various alcohols, aldehydes and primary amines into the corresponding nitriles in excellent yields was easily achieved by trichloroisocyanuric acid (TCCA) as an oxidant and reagent in aqueous ammonia. Also, various benzylic halides were smoothly and directly converted into the corresponding aromatic nitriles in high yields under the same conditions.

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Direct oxidative conversion of alkyl halides into nitriles with molecular iodine and 1,3-diiodo-5,5-dimethylhydantoin in aq ammonia

Cited by 54 publications

References 27 publications

Enhanced Structural Variety of Nonplanar <i>N</i>-Oxyl Radical Catalysts and Their Application to the Aerobic Oxidation of Benzylic C–H Bonds

Enhanced Structural Variety of Nonplanar <i>N</i>-Oxyl Radical Catalysts and Their Application to the Aerobic Oxidation of Benzylic C–H Bonds

Design and synthesis of a magnetic hierarchical porous organic polymer: A new platform in heterogeneous phase‐transfer catalysis

Direct Oxidative Conversion of Alcohols, Amines, Aldehydes, and Benzyl Halides into the Corresponding Nitriles with Trichloroisocyanuric Acid in Aqueous Ammonia

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