Synthesis of ketones by oxidation of alcohols
A ternary hybrid catalyst system comprising a photoredox catalyst, a thiophosphate organocatalyst, and a nickel catalyst enables an acceptorless dehydrogenation of aliphatic secondary alcohols to ketones under visible light irradiation at room temperature in high yield without producing side products (except H2 gas).
H. Fuse, H. Mitsunuma, M. Kanai, J. Am. Chem. Soc., 2020, 142, 4493-4499.
2-Iodoxybenzenesulfonic acid, which can be generated in situ from 2-iodobenzenesulfonic acid sodium salt, is a much more active catalyst than modified IBXs for the oxidation of alcohols with Oxone. Highly efficient and selective methods for the oxidation of alcohols to carbonyl compounds such as aldehydes, carboxylic acids, and ketones were established.
M. Uyanik, M. Akakura, K. Ishihara, J. Am. Chem. Soc., 2009, 131, 251-262.
An efficient bismuth tribromide catalyzed oxidation of various alcohols with aqueous hydrogen peroxide provides carbonyl compounds in good yields.
M.-k. Han, S. Kim, S. T. Kim, J. C. Lee, Synlett, 2015, 26, 2434-2436.
Oxidation of primary and secondary alcohols, using catalytic amounts of TEMPO and tetra-n-butylammonium bromide in combination with periodic acid and wet alumina in dichloromethane is compatible with a broad range of functional groups and acid-sensitive protecting groups. The system also enables a chemoselective oxidation of secondary alcohols in the presence of primary alcohols.
M. Attoui, J.-M. Vatèle, Synlett, 2014, 25, 2923-2927.
Sodium hypochlorite pentahydrate crystals with very low NaOH and NaCl contents oxidize primary and secondary alcohols to the corresponding aldehydes and ketones in the presence of TEMPO/Bu4NHSO4 without pH adjustment. This new oxidation method is also applicable to sterically hindered secondary alcohols.
T. Okada, T. Asawa, Y. Sugiyama, M. Kirihara, T. Iwai, Y. Kimura, Synlett, 2014, 25, 596-598.
The combination of Fe(NO3)3·9H2O and 9-azabicyclo[3.3.1]nonan-N-oxyl enables an efficient aerobic oxidation of a broad range of primary and secondary alcohols to the corresponding aldehydes and ketones at room temperature with ambient air as the oxidant.
L. Wang, S. Shang, G. Li, L. Ren, Y. Lv, S. Gao, J. Org. Chem., 2016, 81, 2189-2193.
Cu/TEMPO catalyst systems show reduced reactivity in aerobic oxidation of aliphatic and secondary alcohols. A catalyst system consisting of (MeObpy)CuOTf and ABNO mediates aerobic oxidation of primary, secondary allylic, benzylic, and aliphatic alcohols with nearly equal efficiency. The catalyst exhibits broad functional group compatibility, and most reactions are complete within 1 h at room temperature using ambient air as oxidant.
J. E. Steves, S. S. Stahl, J. Am. Chem. Soc., 2013, 135, 15742-15745.
A stable nitroxyl radical class of catalysts, 2-azaadamantane N-oxyl (AZADO) and 1-Me-AZADO, exhibit superior catalytic proficiency to TEMPO, converting various sterically hindered alcohols to the corresponding carbonyl compounds in excellent yields.
M. Shibuya, M. Tomizawa, I. Suzuki, Y. Iwabuchi, J. Am. Chem. Soc., 2006, 128, 8412-8413.
An efficient oxidation of primary alcohols to the corresponding aldehydes can be carried out at room temperature in DCM, using trichloroisocyanuric acid in the presence of catalytic TEMPO: aliphatic, benzylic, and allylic alcohols, and β-amino alcohols are rapidly oxidized without no overoxidation to carboxylic acids. The slow oxidation of secondary carbinols makes the reaction highly chemoselective.
L. De Luca, G. Giacomelli, A. Porcheddu, Org. Lett., 2001, 3, 3041-3043.
The combination of N-hydroxyphthalimide (NHPI), a Co species, and optionally a small amount of a (per)benzoic acid catalyzes highly efficient oxidations of alcohols with oxygen. Primary alcohols are rapidly oxidized to the corresponding carboxylic acids, terminal vic-diols give one carbon less carboxylic acids, while internal vic-diols were selectively oxidized to 1,2-diketones.
T. Iwahama, Y. Yoshino, T. Keitoku, S. Sakaguchi, Y. Ishii, J. Org. Chem., 2000, 65, 6502-6507.
A recyclable, polymeric phosphotungstate catalyst bearing a poly(ethylene oxide-pyridinium) matrix efficiently promoted oxidation of various secondary alcohols, including highly sterically demanding neopentyl alcohols, with hydrogen peroxide, to afford the corresponding carbonyl compounds in up to quantitative yield. The chemoselective oxidation in the presence of primary alcohols was achieved.
Y. M. A. Yamada, C. K. Jin, Y. Uozumi, Org. Lett., 2010, 12, 4540-4543.
A water-soluble Cp*Ir complex bearing a bipyridine-based functional ligand can be used as catalyst for a dehydrogenative oxidation of various primary and secondary alcohols to aldehydes and ketones, respectively without any oxidant. The catalyst can be reused.
R. Kawahara, K.-i. Fujita, R. Yamaguchi, J. Am. Chem. Soc., 2012, 134, 3643-3646.
The choline- and peroxydisulfate-based environmentally benign biodegradable oxidizing task-specific ionic liquid (TSIL) choline peroxydisulfate (ChPS) was synthesized and characterized. This reagent enables a selective oxidation of alcohols to aldehydes/ketones in very good yields and short reaction time under solvent-free mild reaction conditions without overoxidation to acid.
B. L. Gadilohar, H. S. Kumbhar, G. S. Shankarling, Ind. Eng. Chem. Res., 2014, 53, 19010-19018.
In the presence of dimethyl sulfoxide, the Burgess reagent efficiently and rapidly facilitates the oxidation of a broad range of primary and secondary alcohols to their corresponding aldehydes and ketones in excellent yields and under mild conditions. This oxidation can be combined with Wittig olefinations. A mechanism similar to those described for the Pfitzner-Moffatt and Swern oxidations is proposed.
P. R. Sultane, C. W. Bielawski, J. Org. Chem., 2017, 82, 1046-1052.
Swern oxidation using the volatile oxalyl chloride as an activator requires reaction temperatures below -60 °C. 3,3-Dichloro-1,2-diphenylcyclopropene (DDC) can be used as a new activator at −20 °C. This convenient new protocol offers mild and fast reactions. Furthermore, the activator DDC is easy to handle, and diphenylcyclopropenone can be recovered quantitively.
T. Guo, Y. Gao, Z. Li, J. Liu, K. Guo, Synlett, 2019, 30, 329-332.
A mild and efficient oxidation of alcohols with o-iodoxybenzoic acid (IBX) is catalyzed by β-cyclodextrin in a water/acetone mixture (86:14). Various alcohols were oxidized at room temperature in excellent yields.
K. Surendra, N. Srilakshmi Krishnaveni, M. Arjun Reddy, Y. V. D. Nageswar, K. Rama Rao, J. Org. Chem., 2003, 68, 2058-2059.
A convenient method enables the preparation of a silica gel supported TEMPO catalyst. The catalyst prepared from [4-hydroxy-TEMPO + NaCl]/SiO2 was used for an aerobic oxidation of alcohols to carbonyls under mild reaction conditions in the presence of Fe(NO3)3 • 9 H2O. Alcohols were converted to the corresponding carbonyls in good to excellent yields. After a simple filtration, the catalyst can be reused at least six times.
N. Tamura, T. Aoyama, T. Takido, M. Kodomari, Synlett, 2012, 23, 1397-1407.
A nitroxyl-radical-catalyzed oxidation using diisopropyl azodicarboxylate (DIAD) allows the conversion of various primary and secondary alcohols to their corresponding aldehydes and ketones without overoxidation to carboxylic acids. 1,2-Diols are oxidized to hydroxyl ketones or diketones depending on the amount of DIAD used.
M. Hayashi, M. Shibuay, Y. Iwabuchi, J. Org. Chem., 2012, 77, 3005-3009.
The combination of TEMPO and CAN can be used for the aerobic oxidation of benzylic and allylic alcohols into their corresponding carbonyl compounds. However, steric hindrance has been observed to impede the reaction with some substituted allylic systems. The present method is superior to others currently available due to its relatively short reaction times and excellent yields.
S. S. Kim, H. C. Jung, Synthesis, 2003, 2135-2137.
A rapid oxidation of primary and secondary alcohols using catalytic amounts of TEMPO and Yb(OTf)3 in combination with a stoichiometric amount of iodosylbenzene afforded carbonyl compounds in excellent yields without over-oxidation. Oxidation of primary alcohols in the presence of secondary alcohols proceeded with good selectivity.
J.-M. Vatèle, Synlett, 2006, 2055-2058.
A novel, metal-free oxidation system for the catalytic synthesis of aldehydes and ketones using TEMPO and a quarternary ammonium salt as catalysts and Oxone as oxidant proved especially successful for the synthesis of ketones. The mild conditions tolerate even sensitive silyl protective groups which can otherwise be cleaved in the presence of Oxone.
C. Bolm, A. S. Magnus, J. P. Hildebrand, Org. Lett., 2000, 2, 1173-1175.
Catalytic use of o-iodoxybenzoic acid (IBX) in the presence of Oxone as a co-oxidant is demonstrated for the oxidation of primary and secondary alcohols. In addition, the in situ oxidation of 2-iodosobenzoic acid (IBA) and even commercially available 2-iodobenzoic acid (2IBAcid) by Oxone to IBX allows the use of these less hazardous reagents, in place of potentially explosive IBX, as catalytic oxidants.
A. P. Thottumkara, M. S. Bowsher, T. K. Vinod, Org. Lett., 2005, 7, 2933-2936.
A highly efficient 2,2,6,6-tetramethylpiperidin-1-yloxy (TEMPO) catalyzed reaction using recyclable 1-chloro-1,2-benziodoxol-3(1H)-one as the terminal oxidant allows the conversion of various alcohols to their corresponding carbonyl compounds in high to excellent yields at room temperature in ethyl acetate, which is an environmentally friendly organic solvent.
X.-Q. Li, C. Zhang, Synthesis, 2009, 1163-1169.
A new, green, mild and inexpensive system, I2-KI-K2CO3-H2O, selectively oxidized alcohols to aldehydes and ketones under anaerobic condition in water at 90 °C with excellent yields.
P. Gogoi, D. Konwar, Org. Biomol. Chem., 2005, 3, 3473-3475.
A simple, efficient, and high-yield procedure for the oxidative conversion of alcohols to various types of esters and ketones was successfully carried out with molecular iodine as the oxidant and potassium carbonate.
N. Mori, H. Togo, Tetrahedron, 2005, 61, 5915-5925.
A chemoselective and efficient procedure allows the conversion of benzylic and allylic alcohols into the corresponding carbonyl compounds with sodium nitrate as oxidant in the presence of 3-methylimidazolinium hydrogensulfate.
A. R. Hajipour, F. Rafiee, A. E. Ruoho, Synlett, 2007, 1118-1119.
Keggin-type heteropoly acids revealed high catalytic activity for swift and selective oxidation of various hydroxy functionalities to the corresponding carbonyl groups using ferric nitrate as an oxidant under mild and solvent-free conditions.
H. Firouzabadi, N. Iranpoor, K. Amani, Synthesis, 2003, 408-412.
A combination of FeCl3, L-valine and TEMPO oxidizes a wide range of primary/secondary benzyl, allylic, and heterocyclic alcohols to aldehydes and ketones with good to excellent isolated yields in the presence of oxygen.
G. Zhang, S. Li, J. Lei, G. Zhang, X. Xie, C. Ding, R. Liu, Synlett, 2016, 27, 956-960.
Tetrapropylammonium perruthenate enables oxidations of a wide range of molecules including examples of both double oxidations and selective oxidations. Mechanistic studies and general experimental procedures are reported. In addition several interesting developments in the chemistry of this reagent are outlined: heteroatom oxidation, cleavage reactions and use in sequential reaction processes.
S. B. Ley, J. Norman, W. P. Griffith, S. P. Marsden, Synthesis, 1994, 639-666.
he mild instability of the Ley-Griffith catalyst (TPAP) creates preparation, storage, and reaction reproducibility issues, due to unpreventable slow decomposition. A set of readily synthesized, bench stable, phosphonium perruthenates (ATP3 and MTP3) mirror the reactivity of TPAP, but avoid storage decomposition issues.
P. W. Moore, C. D. G. Read, P. V. Bernhardt, C. M. Williams, Chem. Eur. J., 2018, 24, 4556-4561.
Urea-hydrogen peroxide in the presence of a catalytic amount of magnesium bromide efficiently oxidizes primary and secondary benzylic alcohols into the corresponding aromatic aldehydes and ketones.
H. J. Park, J. C. Lee, Synlett, 2009, 79-80.
A highly efficient and mild procedure for the oxidation of different types of alcohols uses TEMPO as catalyst, iodobenzene dichloride as stoichiometric oxidant, and pyridine as base. Oxidation of 1,2-diols gives α-hydroxy ketones or α-diketones depending on the amount of oxidant used. High yielding procedures for the preparation of iodoarene dichlorides have been developed.
X.-F. Zhao, C. Zhang, Synthesis, 2007, 551-557.
The oxidation of primary and secondary alcohols by sodium percarbonate in the presence of catalytic amounts of both molybdenyl acetylacetonate and Adogen 464 gave fair to high yields of the corresponding carbonyl compounds.
S. Maignien, S. Aït-Mohand, J. Muzart, Synlett, 1996, 439-440.
A chemoselective oxidation of secondary alcohols with IBX/n-Bu4NBr in CH2Cl2-H2O gave ketones in good yields and allowed the oxidation of secondary hydroxyl group even in the presence of primary hydroxyl groups.
C. Kuhakarn, K. Kittigowittana, M. Pohmakotr, V. Reutrakul, Tetrahedron, 2005, 61, 8995-9000.
Permanganate supported on active manganese dioxide can be used effectively for the oxidation of arenes, alcohols and sulfides under heterogeneous or solvent-free conditions.
A. Shaabania, P. Mirzaeia, S. Naderia, D. G. Leeb, Tetrahedron, 2004, 60, 11415-11420.
Benzyl alcohols and benzyl TBDMS ethers were efficiently oxidized to the corresponding carbonyl compounds in high yield with periodic acid catalyzed by CrO3 at low temperature (-78 °C). The oxidation procedure was highly functional group tolerant and very selective for the TBDMS group over the TBDPS group.
S. Zhang, L. Xu, M. L. Trudell, Synthesis, 2005, 1757-1760.
Pd/C in aqueous alcohol with molecular oxygen, sodium borohydride, and potassium carbonate efficiently oxidized benzylic and allylic alcohols. Sodium borohydride allows a remarkable reactivation of active sites of the Pd surface.
G. An, M. Lim, K.-S. Chun, H. Rhee, Synlett, 2007, 95-98.
A new, highly recoverable palladium-based catalyst for the aerobic oxidation of alcohols combines an organic ligand and mesoporous channels that led to enhanced activity, prevention of agglomeration and the generation of a durable catalyst.
B. Karimi, S. Abedi, J. H. Clark, V. Budarin, Angew. Chem. Int. Ed., 2006, 45, 4776-4779.
A robust and effective Pd catalyst for the aerobic oxidation of various alcohols has been discovered. Using a slightly higher concentration of acetic acid as additive and extending the reaction times, the oxidation can be carried out under ambient atmosphere of air.
D. R. Jensen, M. J. Schultz, J. A. Mueller, M. S. Sigman, Angew. Chem. Int. Ed., 2003, 42, 3810-3813.
[dibmim][BF4] can be used for the oxidation of alcohols to carbonyl compounds. This oxidizing agent offers a high degree of selectivity for the oxidation of primary alcohols to carbonyl compounds without oxidation to carboxylic acids in ionic liquids. [dibmim][BF4] can be reused after oxidation with peracetic acid.
W. Qian, E. Jin, W. Bao, Y. Zhang, Angew. Chem. Int. Ed., 2005, 44, 952-955.
ReOCl3(PPh3)2 catalyzes a rapid oxidation of secondary alcohols by DMSO in the presence of ethylene glycol and refluxing toluene to provide the corresponding ketals in very good yields. Methyl sulfide and water as byproducts of the reaction are easily removed.
J. B. Arterburn, M. C. Perry, Org. Lett., 1999, 1, 769-771.
A practical aerobic oxidation of propargylic alcohols using Fe(NO3)3•9H2O, TEMPO and sodium chloride in toluene at room temperature allows the conversion of propargylic alcohols to α,β-unsaturated alkynals or alkynones in good to excellent yields. This protocol can also be applied in industrial-scale production.
J. Liu, X. Xie, S. Ma, Synthesis, 2012, 44, 1569-1576.
A highly efficient oxidation of propargylic alcohols to ynones is catalyzed by copper nanoparticles (Cu Nps) with TBHP or air as oxidants. With bipyridine as the ligand, the reaction was accelerated significantly and led in good to excellent yields to a variety of propargylic alcohols.
C. Han, M. Yu, W. Sun, Y. Yao, Synlett, 2011, 2363-2368.
A practical and environmentally friendly method for the oxidative rearrangement of five- and six-membered cyclic tertiary allylic alcohols to α,β-unsaturated β-disubstituted ketones by IBX in DMSO is described. Several conventional protecting groups (e.g., Ac, MOM, and TBDPS) are tolerated.
M. Shibuya, S. Ito, M. Takahashi, Y. Iwabuchi, Org. Lett., 2004, 6, 4303-4306.
An efficient oxidant-free oxidation for a wide range of alcohols was achieved by a recyclable ruthenium catalyst, which was prepared from readily available reagents through nanoparticle generation and gelation.
W.-H. Kim, I. S. Park, J. Park, Org. Lett., 2006, 8, 2543-2545.
Adsorbed [RuCl2(p-cymene)]2 on activated carbon is an efficient, environmentally attractive and highly selective catalyst for use in aerobic oxidations, hydrolytic oxidations and dehydrations. The heterogeneous catalyst was recovered quantitatively by simple filtration and could be reused with minimal loss of activity.
E. Choi, C. Lee, Y. Na, S. Chang, Org. Lett., 2002, 4, 2369-2371.
A simple and mild TEMPO-CuCl catalyzed aerobic oxidation of primary and secondary alcohols in ionic liquid [bmim][PF6] gave the corresponding aldehydes and ketones with no trace of overoxidation to carboxylic acids. The product can be isolated by a simple extraction with organic solvent, and the ionic liquid can be recycled or reused.
I. A. Ansari, R. Gree, Org. Lett., 2002, 4, 1507-1509.
Oxidation of alcohols to aldehydes and ketones were performed under atmospheric oxygen with a catalytic amount of V2O5 in toluene at 100°C. Secondary alcohols can be chemoselectively converted into ketones in the presence of primary hydroxy groups.
S. Velusamy, T. Punniyamurthy, Org. Lett., 2004, 6, 217-219.
Benzylic ethers are oxidatively cleaved by 4-acetamido-2,2,6,6-tetramethylpiperidine-1-oxoammonium tetrafluoroborate in wet MeCN at room temperature to give the corresponding aromatic aldehydes and alcohols in high yield. Primary and secondary alkyl alcohols are further oxidized to give carboxylic acids and ketones, respectively.
P. P. Pradhan, J. M. Bobbitt, W. F. Bailey, J. Org. Chem., 2009, 74, 9501-9504.
Trihaloacetic acids can been converted to trichloromethyl and tribromomethyl ketones in good yield by a catalyzed reaction with aldehydes followed by oxidation. A coupling of organozinc intermediates with trichloroacetyl chloride gives trichloromethyl ketones.
E. J. Corey, J. O. Link, Y. Shao, Tetrahedron Lett., 1992, 33, 3435-3438.
A green, practical, convenient, and cheap copper-catalyzed oxidative coupling of aromatic alcohols and acetonitrile to β-ketonitriles involves a C-C coupling with loss of two hydrogen atoms from the corresponding two carbons, using oxygen as the terminal oxidant.
J. Shen, D. Yang, Y. Liu, S. Qin, J. Zhang, J. Sun, C. Liu, C. Liu, X. Zhao, C. Chu, R. Liu, Org. Lett., 2014, 16, 350-353.
Formation of a bromo radical through the oxidation of bromide under mild conditions enables an oxidative debenzylation of N-benzyl amides and O-benzyl ethers to provide the corresponding amides and carbonyl compounds in high yields.
K. Moriyama, Y. Nakamura, H. Togo, Org. Lett., 2014, 16, 3812-3815.
A sequential one-pot synthesis for the oxidation of primary and secondary tert-butyldimethylsilyl (TBDMS) ethers, using the presence of PhIO or PhI(OAc)2 and catalytic amounts of metal triflates and TEMPO in THF or acetonitrile tolerates acid-sensitive protecting groups and leaves tert-butyldiphenylsilyl ethers and phenolic TBDMS groups untouched.
B. Barnych, J.-M. Vatèle, Synlett, 2011, 2048-2052.
A direct retro-Barbier fragmentation of cyclic tertiary alcohols proceeds under mild conditions in the presence of bromine and potassium carbonate in chloroform to provide bromoketones in high yields.
W.-C. Zhang, C.-J. Li, J. Org. Chem., 2000, 65, 5831-5833.
A metal-free ring opening/halogenation of cycloalkanols, which combines both PPO/TBAX oxidant system and blue LEDs irradiation, provides diverse γ, δ, and even more remotely halogenated ketones in good yields under mild conditions.
R. Zhao, Y. Yao, D. Zhu, D. Chang, Y. Liu, L. Shi, Org. Lett., 2018, 20, 1228-1231.