A remarkable effect of ionic liquids in transition-metal-free aerobic oxidation of benzylic alcohols

The transition-metal-free aerobic oxidation of benzylic alcohols is uniquely accelerated by a 1-butyl-3-methylimidazolium hexafluorophosphate (BMI-PF₆)/PhCF₃ biphasic system and Cs₂CO₃ to afford the corresponding ketones in good yields. The reaction system is also applicable to an oxidative cross-esterification of primary benzyl alcohols with a higher aliphatic alcohol.     

Benzylic Bromination of Toluene Derivatives with Boron Tribromide

A facile method for the benzylic bromination of toluene derivatives was developed. Various substituted toluenes were brominated with boron tribromide as bromine source in carbon tetrachloride at room temperature, affording their corresponding benzyl bromides in good yields.     

NaIO4/LiBr-mediated diastereoselective dihydroxylation of olefins: a catalytic approach to the Prevost-Woodward reaction

[reaction: see text] LiBr catalyzes efficiently the dihydroxylation of alkenes to afford syn and anti diols with excellent diastereoselectivity depending upon the use of NaIO(4) (30 mol %) or PhI(OAc)(2) (1 equiv), respectively, as the oxidants. The oxidation of non-benzylic halides has been achieved for the first time to afford the corresponding diols in excellent yields.     

A novel and selective oxidation of benzylic alcohols with polymer-supported periodic acid under mild aprotic conditions

A new polymeric oxidizing reagent was prepared by supporting periodic acid on poly（1,4-phenylene-2,5-pyridine dicarboxyamide）. This polymeric reagent was used for the selective oxidation of primary benzylic alcohols to the corresponding benzaldehydes in CH₃CN at reflux conditions.Excellent selectivity was observed between primary benzyl alcohols and secondary ones as well as non-benzylic alcohols in the oxidation reactions.Allylic alcohols were also converted to the corresponding aldehydes with good yields.     

A mild and efficient method for the oxidation of benzylic alcohols by two-phase electrolysis

Electrochemical oxidation of benzylic and substituted benzylic alcohols by two-phase electrolysis yields the corresponding aldehydes as products. The reaction was carried out in a single compartment cell with platinum electrodes at room temperature in chloroform using an aqueous sodium bromide solution (25%) containing a catalytic amount of HBr. The two-phase electrolysis resulted in high yields (74-96%) of benzaldehyde from primary alcohols and secondary alcohols were oxidized to the corresponding ketone but only in low yields under these conditions.     

离子液体-水介质中离子液体负载TEMPO催化选择氧化合成脂肪醇羟基芳香醛和酮

由于脂肪醇羟基和苄醇羟基具有相同的氧化反应活性,所以当分子内同时含有脂肪醇羟基和苄醇羟基时,很难选择氧化苄醇羟基合成含脂肪醇羟基的芳香醛或酮。本文报道了在离子液体-水介质中,NCS/NaBr/IL-TEMPO（离子液体负载TEMPO）催化氧化合成含有脂肪醇羟基的芳香醛、酮的方法,反应条件温和,选择性好,收率高,且离子液体和催化剂可以循环使用。     

An environmentally benign benzylic oxidation catalyzed by hypervalent iodine intermediate in water

An effective and environmentally benign benzylic oxidation for transition of alkylarenes into the corresponding carbonyl compounds was reported.Alkylarenes were mixed and stirred with potassium bromide,m-chloroperbenzoic acid and a catalytic amount of iodobenzene in water at 60 8C for several hours,a series of the corresponding carbonyl compounds was obtained in moderate to good yields.In the reaction,iodobenzene was first oxidized by m-chloroperbenzoic acid into the hypervalent iodine intermediate which then reacted with potassium bromide to form the key radical initiator for the benzylic oxidation.     

Application and Mechanistic Studies of a Water‐Oxidation Catalyst in Alcohol Oxidation by Employing Oxygen‐Transfer Reagents

By using a dimeric ruthenium complex in combination with tert‐butyl hydrogen peroxide (TBHP) as stoichiometric oxidant, a mild and efficient protocol for the oxidation of secondary benzylic alcohols was obtained, thereby giving the corresponding ketones in high yields within 4 h. However, in the oxidation of aliphatic alcohols, the TBHP protocol suffered from low conversions owing to a competing Ru‐catalyzed disproportionation of the oxidant. Gratifyingly, by switching to Oxone (2 KHSO₅ ? KHSO₄ ? K₂SO₄ triple salt) as stoichiometric oxidant, a more efficient and robust system was obtained that allowed for the oxidation of a wide range of aliphatic and benzylic secondary alcohols, giving the corresponding ketones in excellent yields. The mechanism for these reactions is believed to involve a high‐valent Ru^V–oxo species. We provide support for such an intermediate by means of mechanistic studies.     

3,3]-Sigmatropic rearrangement/5-exo-dig cyclization reactions of benzyl alkynyl ethers: synthesis of substituted 2-indanones and indenes

Substituted benzyl alkynyl ethers, prepared from the corresponding α-alkoxy ketones in a two-step sequence involving enol triflate formation and KOtBu-induced E2 elimination, undergo [3,3]-sigmatropic rearrangement/intramolecular 5-exo-dig cyclization at 60 °C to form substituted 2-indanones in good overall yields. 1,3-cis-Disubstituted-2-indanones are formed preferentially when the benzylic substituent R(1) is bulky. Substituted indenes may be prepared from 2-indanones in high yields by Horner-Wadsworth-Emmons reaction.     

Chemoselective Oxidation of Benzylic Alcohols and Hydroquinones with bis-(2,4,6-Trimethylpyridinium) Dichromate (BTMPDC) as an Efficient and New Oxidizing Agent

A simple, efficient, and chemoselective oxidation of benzylic alcohols to the corresponding aldehydes and ketones and also hydroquinones to the benzoquinones using bis-(2,4,6-trimethylpyridinium) dichromate (BTMPDC) in acetonitrile is described. A good range of primary and secondary benzylic alcohols and a limited range of hydroquinones were selectively oxidized under reflux conditions in reasonable yields.     

The role of aromatic radical cations and benzylic cations in the 2,4,6-triphenylpyrylium tetrafluoroborate photosensitized oxidation of ring-methoxylated benzyl alcohols in CH2Cl2 solution

A steady-state and laser flash photolysis (LFP) study of the TPPBF(4)-photosensitized oxidation of ring-methoxylated benzyl alcohols has been carried out. Direct evidence on the involvement of intermediate benzyl alcohol radical cations and benzylic cations in these reactions has been provided through LFP experiments. The reactions lead to the formation of products (benzaldehydes, dibenzyl ethers, and diphenylmethanes) whose amounts and distributions are influenced by the number and relative position of the methoxy substituents. This behavior has been rationalized in terms of the interplay between the stabilities of benzyl alcohol radical cations and benzyl cations involved in these processes. A general mechanism for the TPPBF(4)-photosensitized reactions of ring-methoxylated benzyl alcohols has been proposed, where the alpha-OH group of the parent substrate acts as the deprotonating base promoting alpha-C-H deprotonation of the benzyl alcohol radical cation (formed after electron transfer from the benzyl alcohol to TPP) to give a benzyl radical and a protonated benzyl alcohol, precursor of the benzylic cation. This hypothesis is in contrast with previous studies, where formation of the benzyl cation was suggested to occur from the neutral benzyl alcohol through the Lewis acid action of excited TPP(+) (TPP).     

Synthesis of unsymmetrical benzil licoagrodione

A synthesis of unsymmetrical 1,2-diarylethane-1,2-dione is reported involving the intramolecular cyclization of anionic benzylic ester of the aryl benzyl ether followed by oxidation employing dioxirane. With the use of microwave irradiation, licoagrodione was prepared from Claisen rearrangement of the corresponding allyl phenyl ether 1,2-diketone readily available from the Lindlar's reduction of the corresponding alkyne derivative. Subsequent removal of protecting groups then furnished the desired product.     

Aerobic oxidative transformation of primary azides to nitriles by ruthenium hydroxide catalyst

In the presence of an easily prepared supported ruthenium hydroxide catalyst, Ru(OH)(x)/Al(2)O(3), various kinds of structurally diverse primary azides including benzylic, allylic, and aliphatic ones could be converted into the corresponding nitriles in moderate to high yields (13 examples, 65-94% yields). The gram-scale (1 g) transformation of benzyl azide efficiently proceeded to give benzonitrile (0.7 g, 90% yield) without any decrease in the performance in comparison with the small-scale (0.5 mmol) transformation. The catalysis was truly heterogeneous, and the retrieved catalyst could be reused for the transformation of benzyl azide without an appreciable loss of its high performance. The present transformation of primary azides to nitriles likely proceeds via sequential reactions of imide formation, followed by dehydrogenation (β-elimination) to produce the corresponding nitriles. The Ru(OH)(x)/Al(2)O(3) catalyst could be further employed for synthesis of amides in water through the transformation of primary azides (benzylic and aliphatic ones) to nitriles, followed by sequent hydration of the nitriles formed. Additionally, direct one-pot synthesis from alkyl halides and TBAN(3) (TBA = tetra-n-butylammonium) could be realized with Ru(OH)(x)/Al(2)O(3), giving the corresponding nitriles in moderate to high yields (10 examples, 64-84% yields).     

纳米尺度氧化石墨烯层作为高效碳催化剂用于苄醇与芳香醛的绿色氧化

合成了纳米尺度氧化石墨烯(NGO)层,用作碳催化剂高效催化苄醇与芳香醛的氧化反应.对于醇氧化反应,当80℃时H2O2存在下,NGOs(20 wt％)可高效催化醇选择性生成醛,其反应速率和产率取决于醇上取代基的性质.对于4-硝基苄醇,反应24 h后,只有10％可转换为相应羧酸.相反,4-甲氧基苄醇和二苯基甲醇分别反应仅9和3h则可完全转化为对应的羧酸和酮.NGO碳催化剂上芳香醛氧化速率高于醇氧化速率.对于所有的醛,采用7 wt％ NGO作催化剂,在70℃反应2-3 h后,就可完全转化为相应羧酸.我们讨论了NGO催化剂结构对苄醇和芳香醛氧化反应影响的可能机理.     

Ceric Triethylammonium Nitrate [Ce(Et3NH)2l(NO3)6; An Efficient Oxidant for the Oxidation of Benzylic Alcohols and α-Hydroxy Ketones to Their Corresponding Carbonyl Compounds Under Mild Conditions

Ceric triethyl ammonium nitrate is prepared and used for the oxidation of benzylic alcohols, and α-hydroxy Retones to their corresponding carbonyl compounds in methylene chloride with high yields.     

Oxygen transfer reactions. 4. Reaction of high valent oxoruthenium compounds with sulfides

The oxidation of methoxy substituted benzyl phenyl sulfides can be used to distinguish between oxidants that react by single electron transfer (followed by oxygen rebound) and those which react by direct oxygen atom transfer in a two-electron process. Transfer of a single electron results in the formation of an intermediate radical cation, which can undergo C-S bond cleavage and deprotonation reactions leading to the formation of methoxy substituted benzyl derivatives, methoxy substituted benzaldehydes, and diphenyl disulfide. The oxidation of 4-methoxybenzyl phenyl sulfide and 3,4,5-trimethoxybenzyl phenyl sulfide by oxidants known to participate in single electron transfers (Ce(4+), Mn(3+), and Cr(6+)) results in the formation of the corresponding benzaldehydes, benzyl alcohols, benzyl acetates, and benzyl nitrates in variable yields. However, the only products obtained from the oxidation of the same compounds with RuO(4), RuO(4-), and RuO(4)(2-) are sulfoxides and sulfones. Therefore, it is concluded that the oxidation of sulfides by oxoruthenium compounds likely proceeds by a concerted mechanism.     

First example of direct RuO4-catalyzed oxidation of isoxazolidines to 3-isoxazolidones

RuO2/NaIO4 oxidation of 3-unsubstituted isoxazolidines, under ethyl acetate/water biphasic conditions, affords 3-isoxazolidones in good yields. The methodology can be used on both racemic and optically active isoxazolidines.     

Efficient synthesis of carbonyl compounds: oxidation of azides and alcohols catalyzed by vanadium pentoxide in water using tert-butylhydroperoxide

Catalytic amount of vanadium reagent with tert-butylhydroperoxide as the oxidant was found to be an excellent oxidizing agent in aqueous medium. Vanadium pentoxide with aq tert-butylhydroperoxide readily oxidizes primary benzylic azides to the corresponding acids and secondary benzylic azides to the corresponding ketones in excellent yields. Further, vanadium pentoxide and aq tert-butylhydroperoxide combination turned out to be an effective catalyst for the oxidation of alcohols. Using vanadium pentoxide and aq tert-butylhydroperoxide primary alcohols were oxidized to the corresponding acids, whereas secondary alcohols underwent a smooth transformation to furnish corresponding ketones in excellent yields. All the oxidations are performed in water.     

Synthesis of benzylic boronates via palladium-catalyzed cross-coupling reaction of bis(pinacolato)diboron with benzylic halides

The palladium cross-coupling reaction of benzyl halides with diboron 1 yielded structurally diverse pinacol benzylic boronates. Under these reaction conditions, sensitive functionalities such as esters and nitriles are tolerated and the benzylic boronates are obtained in good to high yields.     

Aerobic photocatalytic oxidation of activated benzylic and allylic alcohols to carbonyl compounds catalyzed by molecular iodine

An efficient, selective and environmentally benign photocatalytic system in acetonitrile has been developed for aerobic oxidation of activated benzylic and allylic alcohols into their corresponding aldehydes and ketones without the need for a transition metal in moderate to excellent yields with a catalytic amount of iodine. Very high inter- and intramolecular chemoselectivities are observed when benzylic OH groups are oxidized in the presence of aliphatic (nonbenzylic) hydroxyls.