不得不知的有机氧化剂(英文).docx

one 、mcpba3-chloroperoxybenzoic acid, mcpba, meta-chloroperbenzoic acidmcpba is a strong oxidizing agent, which is comparable with other peracids. advantages of 3-chloroperbenzoic acid is its handling, because it is present as powder, which can be kept in the refrigerator. nevertheless, material of purity 75% is rarely available commercially, since the pure compound is not particularly stable. therefore the transport in airplanes with a content of 72% is forbidden. main pollution is 3-chlorobenzoic acid (10%) as well as for safety reasons water. mcpba is versatile applicable as peracid for use in laboratories. main areas are the oxidation of aldehydes and ketones to esters (bayer-villiger-oxidation) olefines to epoxides sulfides to sulfoxides and sulfones amines to nitroalkanes, nitroxides or n-oxides however, for reasons of the atomic economy, the use of mcpba in production should be avoided. the research concentrates within this area rather on the use of hydrogen peroxide in connection with suitable catalysts or in situ generated, simpler peracids, such as peracetic acid or on potassium peroxymonosulfate (oxone). in many reactions mcpba with an outstanding reactivity is however more selective than hydrogen peroxide and other peracids.name reactionscope eliminationprilezhaev reactionrubottom oxidationrecent literatureuse of a solvent with greater density than the fluorous phase is an alternative to the u-tube method in phase-vanishing reactions in cases where both reactants are less dense than the fluorous phase.n. k. jana, j. g. verkade, org. lett., 2003, 5, 3787-3790.n. k. jana, j. g. verkade, org. lett., 2003, 5, 3787-3790.n. k. jana, j. g. verkade, org. lett., 2003, 5, 3787-3790.the results of a highly diastereoselective epoxidation of allylic diols derived from baylis-hillman adducts are reported.r. s. porto, m. l. a. a. vasconcellos, e. ventura, f. coelho, synthesis, 2005, 2297-2306.a clean and efficient and metal-free diacetoxylation reaction of alkenes using commercially available peroxyacids as the oxidants is catalyzed by triflic acid. this method enables also oxidative lactonizations of unsaturated carboxylic acids in good to high yields.y.-b. kang, l. h. gade, j. org. chem., 2012, 77, 1610-1615.sequential treatment of a 1,2-disubstituted olefin with m-cpba, br3cco2h, and dbu results in the one-pot, stereospecific conversion of the olefin to the corresponding disubstituted cyclic carbonate. when a solution of a secondary allylic or homoallylic amine and br3cco2h is sequentially treated with m-cpba then dbu, the product of the reaction is a cyclic carbamate.s. g. davies, a. m. fletcher, w. kurosawa, j. a. lee, g. poce, p. m. roberts, j. e. thomson, d. m. williamson, j. org. chem., 2010, 75, 7745-7756.several amides were obtained in high yields by an efficient method from the corresponding imines which are readily prepared from aldehydes. this procedure involves the oxidation of aldimines with m-cpba and bf3oet2. in this reaction, the product is strongly influenced by the electron releasing capacity of the aromatic substituent (ar).g. an, m. kim, j. y. kim, h. rhee, tetrahedron lett., 2003, 44, 2183-2186.an efficient oxidation of cyclic acetals provided hydroxy alkyl esters in good yields in the presence of mcpba.j. y. kim, h. rhee, m. kim, j. korean chem. soc., 2002, 46, 479-483.various ketones could be reacted into -tosyloxy ketones in the presence of mcpba, ptsah2o, catalytic amounts of iodine and tert-butylbenzene in a mixture of acetonitrile and 2,2,2-trifluoroethanol. in the reaction, 4-tert-butyl-1-iodobenzene is formed at first and then converted into the -tosyloxylation reagent 4-tert-butyl-1-(hydroxy)(tosyloxy)iodobenzene by the reaction with mcpba and ptsah2o.a. tanaka, k. moriyama, h. togo, synlett, 2011, 1853-1854.various -tosyloxyketones were efficiently prepared in high yields from the reaction of ketones with m-chloroperbenzoic acid and p-toluenesulfonic acid in the presence of a catalytic amount of iodobenzene.y. yamamoto, h. togo, synlett, 2006, 798-800.reaction of methyl sulfinates with lithium amides followed oxidation of the resulting sulfinamides provides primary, secondary, and tertiary alkane-, arene- and heteroarenesulfonamides in high yields. this protocol avoids the use of hazardous, unstable, or volatile reagents and does not affect the configurational stability of the amines.j. l. c. ruano, a. parra, f. yuste, v. m. mastranzo, synthesis, 2008, 311-312.-piperidinoethylsulfides can be oxidized by m-chloroperbenzoic acid to intermediates containing both n-oxide and sulfone functions. these undergo a cope-type elimination to a vinylsulfone that can be captured by amines to afford -aminoethylsulfones. the synthetic methodology developed can be utilized in multiple-parallel format and has numerous potential applications in medicinal chemistry.r. j. gruffin, a. henderson, n. j. curtin, a. echalier, j. a. endicott, i. r. hardcastle, d. r. newell, m. e. m. noble, l.-z. wang, b. t. golding, j. am. chem. soc., 2006, 128, 6012-6013.the synthesis of n-cyanosulfilimines can readily be achieved by reaction of the corresponding sulfides with cyanogen amine in the presence of a base and nbs or i2 as halogenating agents. oxidation followed by decyanation affords synthetically useful sulfoximines.o. garca mancheo, o. bistri, c. bolm, org. lett., 2007, 9, 3809-3811.iodobenzene can be used as a recyclable catalyst in combination with m-chloroperbenzoic acid as the terminal oxidant for an efficient and regioselective monobromination of electron-rich aromatic compounds. the bromination of electron-rich aromatic compounds with lithium bromide was fast in tetrahydrofuran at room temperature, providing regioselective monobrominated products in good yields.z. zhou, x. he, synthesis, 2011, 207-209.a new, regiospecific, sequential one-pot synthesis of symmetrical and unsymmetrical diaryliodonium tetrafluoroborates, which are the most popular salts in metal-catalyzed arylations, is fast and high-yielding and has a large substrate scope. furthermore, the corresponding diaryliodonium triflates can conveniently be obtained via an in situ anion exchange.m. bielawski, d. aili, b. olofsson, j. org. chem., 2008, 73, 4602-4607.one-pot syntheses of neutral and electron-rich hydroxy(tosyloxy)iodoarenes (htibs) from iodine and arenes avoid the need for expensive iodine(iii) precursors. a large set of htibs, including a polyfluorinated analogue, can be obtained from the corresponding aryl iodides under mild conditions, without excess reagents, in high yields.e. a. merritt, v. m. t. carneiro, l. f. silva jr., b. olofsson, j. org. chem., 2010, 75, 7416-7419.a direct synthesis of symmetric and unsymmetric electron-rich diaryliodonium salts delivers diaryliodonium tosylates in high yields using mcpba and toluenesulfonic acid. an in situ anion exchange has also been developed, giving access to the corresponding triflate salts.m. zhu, n. jalalian, b. olofsson, synlett, 2008, 592-596. two、jones试剂jones reagentthe jones reagent is a solution of chromium trioxide in diluted sulfuric acid that can be used safely for oxidations of organic substrates in acetone. the reagent can also be prepared from sodium dichromate and potassium dichromate. jones reagent is especially suitable for the oxidation of secondary alcohols to ketones and of primary alcohols to carboxylic acids and in a few cases to aldehydes (jones oxidation). some alternative chromium reagents allow the selective preparation of aldehydes, such as pcc and pdc.although the reagent is very acidic, the substrate in acetone is essentially titrated with the oxidant solution and only very acid-sensitive groups are incompatible. for example esters, even tert-butyl esters, remain unchanged. the concentration of sulfuric acid can be decreased to minimize side reactions, although the oxidation power increases too.a full review of chromium-based reagents can be found in the book written by tojo and fernndez (oxidation of alcohols to aldehydes and ketones, springer berlin, 2006, 1-97.).attention: chromium (vi) compounds are toxic and must be handled with care.name reactionsjones oxidationjones oxidationrecent literatureselective oxidation of allylic alcohols with chromic acidk. e. harding, l. m. may, k. f. three、dess-martin periodinanedess-martin periodinanethe dess-martin periodinane (dmp) is commercially available and decomposes only slowly. but dmp is heat- and shock-sensitive, and shows an exotherm when heated 130 c. 2-iodoxybenzoic acid (ibx), the impact-sensitive intermediate in the synthesis of the dess-martin periodinane, is available in a dmso solution and is also used as an oxidizing agent.name reactionsdess-martin-oxidationrecent literaturepartial hydrolysis of dmp or incomplete acetylation gives a more effective oxidant, explaining why impure samples of dmp in many cases provide better results than the pure reagent. when reliable and convenient rate enhancement is desired, pure dmp may be decomposed with an equivalent of water immediately before or during its use.s. d. meyer, s. l. schreiber, j. org. chem., 1994, 59, 7549-7552.alcohols are oxidized to the corresponding carbonyl compounds with iodoxybenzoic acid (ibx) or with dess-martin-periodinane (dmp) in bmimbf4 and bmimpf6 ionic liquids at room temperature in excellent yields with high selectivity. these oxidations are faster in ionic liquids as compared to conventional solvents. the byproduct iodosobenzoic acid (iba) and the ionic liquid are readily recovered.j. s. yadav, b. v. s. reddy, a. k. basak, a. v. narsaiah, tetrahedron, 2004, 60, 2131-2135.among the reported examples of new reactivity of the hypervalent iodine reagent dmp (dess-martin periodinane) are the one-step oxidation of secondary amides to imides and n-acyl vinylogous carbamates or ureas and the direct oxidation of benzylic and related primary amines to the corresponding nitriles.k. c. nicolaou, c. j. n. mathison, angew. chem. int. ed., 2005, 44, 5992-5997.k. c. nicolaou, c. j. n. mathison, angew. chem. int. ed., 2005, 44, 5992-5997.k. c. nicolaou, c. j. n. mathison, angew. chem. int. ed., 2005, 44, 5992-5997.dess-martin periodine in combination with organosulfonic acids reacted with ketones and dicarbonyl compounds under reflux temperature in acetonitrile to give -organosulfonyloxylated compounds in good yields.u. s. mahajan, k. g. akamanchi, synlett, 2008, 987-990.dess-martin periodinane (dmp) efficiently mediates the intramolecular cyclization of phenolic azomethines at ambient temperature leading to substituted benzoxazoles and benzothiazoles. treatment of the reaction mixtures sequentially with amberlyst a-26 thiosulfate resin and diisopropylaminomethyl resin (ps-diea) removes excess reagent and byproducts, to give pure products.d. s. bose, m. idrees, synthesis, 2010, 398-402.a new, mild, and efficient method for the synthesis of 2-substituted benzothiazoles proceeds via the intramolecular cyclization of thioformanilides by using hypervalent iodine reagents in ch2cl2 at ambient temperature.d. s. bose, m. idrees, j. org. chem., 2006, 71, 8261-8263. four、hydrogen peroxidehydrogen peroxidesee also: hydrogenperoxide urea adduct, sodium perborate, sodium percarbonatename reactionsbaeyer-villiger oxidationfollow-up reaction of brown hydroborationozonolysisrecent literaturea clean and safe method for the dihydroxylation of alkenes under organic-solvent- and metal-free conditions was developed. the resin-supported sulfonic acid is easily recycled.y. usui, k. sato, m. tanaka, angew. chem. int. ed., 2003, 42, 5623-5625.convenient methods for the preparation of stable and non-volatile mono- and dichloroborane adducts of dioxane from dioxane-bcl3 and nabh4 in the presence of catalytic amounts of tri- or tetraglyme were developed. the dioxane-monochloroborane adduct hydroborates representative olefins cleanly and rapidly and lead to the corresponding alcohols in quantitative yields after oxidation.j. v. b. kanth, h. c. brown, j. org. chem, 2001, 66, 5359-5365.a rhodium-catalyzed enantioselective syn addition of bis(catecholato)diboron to simple alkenes in the presence of (s)-quinap provides enantioenriched 1,2-diols after subsequent oxidation. the substrate scope, the reaction mechanism, and competing pathways are discussed.s. trudeau, j. m. morgan, m. shrestha, j. p. morken, j. org. chem., 2005, 70, 9538-9544.pt-catalyzed enantioselective addition of bis(pinacolato)diboron (b2(pin)2) to conjugated dienes enables an asymmetric 1,4-dihydroxylation of 1,3-dienes. dienes which are unable to adopt the s-cis conformation are unreactive. for most substrates, 1,4-addition is the predominant pathway.h. e. burks, l. t. kliman, j. p. morken, j. am. chem. soc., 2009, 131, 9134-9135.a catalytic stereoselective 1,4-diboration of conjugated dienes with b2(pin)2 and the presence of ni(cod)2 and pcy3 as the catalyst roceeds efficiently at low catalyst loadings and broadens the substrate scope of current methods for catalytic diene diboration by including internal and sterically hindered. the intermediate allylboronate was oxidized to the stereodefined allylic 1,4-diol.r. j. ely, j. p. morken, org. lett., 2010, 12, 4348-4351.lithiated epoxides react stereospecifically with boronates to give syn-1,2-diols, a process that can be used iteratively to create triols containing four stereogenic centers.e. vedrenne, o. a. wallner, m. vitale, f. schmidt, v. k. aggarwal, org. lett., 2009, 11, 165-168.a direct, mild ketohydroxylation of various 1-aryl-1-alkenes with h2o2, catalyzed by the inexpensive 12-tungstophosphoric acid/cetylpyridinium chloride system, gave acyloins in good yields and high regioselectivies.y. zhang, z. shen, j. tang, y. zhang, l. kong, y. zhang, org. biomol. chem., 2006, 4, 1478-1482.an efficient epoxidation of a broad range of olefins using hydrogen peroxide as the oxidant has been accomplished in the presence of acetic acid and a manganese catalyst that exhibits an uncommon chemoselectivity.i. garcia-bosch, x. ribas, m. costas, adv. synth. catal., 2008, 351, 348-352.a chiral bisaryl-silyl-protected pyrrolidine acts as a very selective epoxidation organocatalyst using simple oxidation agents. the scope of the reaction is demonstrated by the formation of optically active ,-epoxy aldehydes in high yields and enantioselectivities. the asymmetric epoxidation reactions proceed also under environmental friendly reaction conditions in, for example, water mixtures of alcohols.m. marigo, j. franzen, t. b. poulsen, w. zhuang, k. a. jorgensen, j. am. chem. soc., 2005, 127, 6284-6289.a combined amino- and n-heterocyclic carbene (nhc)-catalyzed one-pot reaction sequence using commercially available catalysts at low catalyst loadings gives -hydroxy and -amino esters in high yield and excellent enantiopurity. the generation of quaternary stereocenters and application in gram-scale synthesis were also realized, with no requirements of inert or anhydrous reaction conditions.h. jiang, b. gschwend, . albrecht, k. a. jrgensen, org. lett., 2010, 12, 5052-5055.an effective epoxidation of lipophilic alkenes using hydrogen peroxide was accomplished with a manganese sulfate/bicarbonate catalytic system in an ionic liquid at room temperature.k.-h. tong, k.-y. wong, t. h. chan, org. lett., 2003, 5, 3423-3425.an epoxidation of alkenes using hydrogen peroxide as the terminal oxidant is promoted by catalytic amounts (1.0-0.1 mol %) of manganese(2+) salts, and must be performed using at least catalytic amounts of bicarbonate buffer. various aryl-substituted, cyclic, and trialkyl-substituted alkenes were epoxidized under these conditions using 10 equiv of hydrogen peroxide, but monoalkyl-alkenes were not. additives such as sodium acetate and salicylic acid enhanced the rate of the desired epoxidation reaction by 2-3 times. possible mechanisms for the reaction are discussed.b. s. lane, m. vogt, v. j. derosa, k. burgess, j. am. chem. soc., 2002, 124, 11946-11954.aryl benzyl selenoxides are efficient catalysts for the epoxidation of various olefinic substrates and the baeyer-villiger oxidation of aldehydes and ketones with hydrogen peroxide.m. a. goodman, m. r. detty, synlett, 2006, 1100-1104.a highly enantioselective catalytic epoxidation of ,-unsaturated diaryl enones was achieved with high chemical yield by using aqueous hydrogen peroxide in the presence of a guanidine-urea bifunctional organocatalyst. the catalyst performs cooperatively by interaction of the guanidine group with hydrogen peroxide and the urea group with the enone or vice versa.s. tanaka, k. nagasawa synlett, 2009, 667-670.chiral primary amine salts catalyze highly enantioselective epoxidations of cyclic enones with hydrogen peroxide.x. wang, c. m. reisinger, b. list, j. am. chem. soc., 2008, 130, 6070-6071.m. a. goodman, m. r. detty, synlett, 2006, 1100-1104.aldehydes undergo oxidative transformation to the methyl esters in methanol as solvent upon treatment with catalytic amounts of vanadium pentoxide in combination with hydrogen peroxide. this method features mild reaction conditions, short reaction times, high efficiencies, cost-effectiveness, and facile isolation of the desired products.r. gopinath, b. patel, org. lett., 2000, 2, 577-579.a convenient and efficient oxidation of hydroxylated and methoxylated benzaldehydes and acetophenones to the corresponding phenols uses hydrogen peroxide and methyltrioxorhenium as catalyst in ionic liquids bmimbf4 and bmimpf6.r. bernini, a. coratti, g. provenzano, g. fabrizi, d. tofani, tetrahedron, 2005, 6