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Synthesis of ketones by cleavage of alkenes


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The OsO4-catalyzed direct oxidation of olefins via the carbon-carbon cleavage of an osmate ester by the action of oxone allows the preparation of ketones or carboxylic acids in high yields. This method should be applicable as an alternative to ozonolysis.
B. R. Travis, R. S. Narayan, B. Borhan, J. Am. Chem. Soc., 2002, 124, 3824-3825.

Catalyzed by Se/Fe via hybrid mechanisms, the carbon-carbon double bond in alkenes can break to produce carbonyls under mild conditions. Since O2 can be used as a partial oxidant, the employed H2O2 amount can be lowered to avoid peroxide residues, making the process even safer for operation.
X. Li, H. Hua, Y. Liu, L. Yu, Org. Lett., 2023, 25, 6720-6724.

Upon addition of B(C6F5)3H2O, the oxidation potential of quinoxalinone increased remarkably, enabling the photoredox aerobic oxidation of alcohols, thiols, and alkenes toward carbonyl compounds and dithioethers under visible light conditions. This combination could serve as a versatile photocatalyst system for both energy transfer and single electron transfer processes.
J. Huang, Y.-X. Luo, L. Wang, X.-Y. Tang, Org. Lett., 2023, 25, 5613-5618.

A light-driven, Mn-catalyzed protocol for the selective oxidation of alkenes to carbonyls under 1 atm of O2 provides ketones and aldehydes under clean, mild conditions. Aromatic as well as various nonactivated aliphatic alkenes could be oxidized with a first row, biorelevant metal catalyst. Moreover, the protocol shows a very good functional group tolerance.
Z. Huang, R. Guan, M. Shanmugam, E. L. Bennett, C. M. Robertson, A. Brookfield, E. J. L. MeInnes, J. Xiao, J. Am. Chem. Soc., 2021, 143, 10005-10013.

CsPbBr3 nanocrystals catalyze a facile visible-light-driven oxidative cleavage of C=C bonds to the corresponding carbonyls. This catalytic system was applicable to a wide range of terminal and internal alkenes.
Q. Fan, H. Zhang, D. Liu, C. Yan, H. Zhu, Z. Xie, Z. Le, J. Org. Chem., 2023, 88, 7391-7400.

N-hydroxyphthalimide (NHPI) catalyzes a metal-free, aerobic oxidative cleavage of olefins. This methodology avoids the use of toxic metals or overstoichiometric amounts of traditional oxidants, showing good economical and environmental advantages. Based on the experimental observations, a plausible mechanism is proposed.
R. Lin, F. Chen, N. Jiao, Org. Lett., 2012, 14, 4158-4161.

Sodium benzene sulfinate catalyzed a visible-light-driven aerobic oxidative cleavage of olefins to provide the corresponding aldehydes and ketones under transition-metal-free conditions. Notably, α-halo-substituted styrenes proceeded with photoinduced oxidation to finally afford α-halo-acetophenones with halogen migration.
Y.-X. Chen, J.-T. He, M.-C. Wu, Z.-L. Liu, K. Tang, P.-J. Xia, K. Chen, H.-Y. Xiang, X.-Q. Chen, H. Yang, Org. Lett., 2022, 24, 3920-3925.

A mild and operationally simple protocol for the selective aerobic oxidation of aromatic olefins to carbonyl compounds is catalyzed by a Fe(III) species bearing a pyridine bisimidazoline ligand at 1 atm of O2. The method cleaves α- and β-substituted styrenes to afford benzaldehydes and aromatic ketones in high yields with excellent chemoselectivity and very good functional group tolerance.
A. Gonzalez-de-Castro, J. Xiao, J. Am. Chem. Soc., 2015, 137, 8206-8218.

In a 2,2-azobis(isobutyronitrile)-catalyzed oxidative cleavage of gem-disubstituted alkenes with molecular oxygen as the oxidant, carbonyl compounds were obtained as the desired products in high yield under mild conditions.
G.-Z. Wang, X.-L. Li, J.-J. Dai, H.-J. Xu, J. Org. Chem., 2014, 79, 7220-7225.

The use of nitroarenes as oxygen transfer reagents enables an anaerobic cleavage of a wide range of alkenes possessing oxidatively sensitive functionalities into carbonyl compounds under visible light irradiation. This approach serves as a safe and practical alternative to mainstream oxidative cleavage protocols, such as ozonolysis and the Lemieux-Johnson reaction.
D. E. Wise, E. S. Gogarnoiu, A. D. Duke, J. M. Paolillo, T. L. Vacala, W. A. Hussain, M. Parasram, J. Am. Chem. Soc., 2022, 144, 15437-15442.

A gold(I)-catalyzed oxidative cleavage of alkenes with tert-butyl hydrogenperoxide (TBHP) as the oxidant in the presence of neocuproine afforded ketones or aldehydes as products.
D. Xing, B. Guan, G. Cai, Z. Fang, L. Yang, Z. Shi, Org. Lett., 2006, 8, 693-696.

Specific oxidation protocols have been developed for the cleavage of styrenes, aliphatic olefins, and terminal aliphatic olefins to carbonyl compounds with ruthenium trichloride as catalyst. Olefins that are not fully substituted are converted to aldehydes rather than carboxylic acids.
D. Yang, C. Zhang, J. Org. Chem., 2001, 66, 4814-4818.

A catalytic amount of a composite material, RuO2/BaTi4O9, in combination with NaIO4 in EtOAc-H2O has been shown to efficiently cleave alkenes, affording ketones, aldehydes and/or carboxylic acids in high yields.
H. Okumoto, K. Ohtsuko, S. Banjoya, Synlett, 2007, 3201-3205.

Osmium tetroxide has been microencapsulated in a polyurea matrix. These microcapsules have been effectively used as recyclable catalysts in the dihydroxylation and the oxidative cleavage of olefins.
S. V. Ley, C. Ramarao, A.-L. Lee, N. Ostergaard, S. C. Smith, I. M. Shirley, Org. Lett., 2003, 5, 185-187.

An iron-sulfur complex formed by the simple mixture of FeCl3 with S3- generated in situ from K2S mediates an aerobic oxidation of terminal alkenes under an atmosphere of O2 (balloon). The reaction could proceed on a gram scale, expanding the application of S3- in organic synthesis.
J.-J. Ai, B.-B. Liu, J. Li, F. Wang, C.-M. Huang, W. Rao, S.-Y. Wang, Org. Lett., 2021, 23, 4705-4709.

The use of PhI(OAc)2 in dichloromethane enables a clean oxidative cleavage of 1,2-diols to aldehydes. In the presence of OsO4 as catalyst, NMO and 2,6-lutidine, olefinic bonds can be cleaved in acetone/water to yield the corresponding carbonyl compounds.
K. C. Nicolaou, V. A. Adsool, C. R. H. Hale, Org. Lett., 2010, 12, 1552-1555.

The oxidative cleavage of C=C bonds adjacent to aryl and alkyl moieties was efficiently achieved with monoacetylated bishydroperoxides. Base-mediated fragmentation of monoacetylated bishydroperoxides generates singlet molecular oxygen as active oxidant in situ. All the reactions furnished the respective carbonyl compounds in good yields at room temperature within short reaction times.
D. Azarifar, Z. Najminejad, Synlett, 2013, 24, 1377-1382.