Chemistry:Alcohol oxidation

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Alcohol oxidation is a collection of oxidation reactions in organic chemistry that convert alcohols to aldehydes, ketones, carboxylic acids, and esters where the carbon carries a higher oxidation state. The reaction mainly applies to primary and secondary alcohols. Secondary alcohols form ketones, while primary alcohols form aldehydes or carboxylic acids.[1]

The reaction can occur using a variety of oxidants.

Stages in the oxidation of primary alcohols to carboxylic acids via aldehydes and aldehyde hydrates

In principle, a simple way to oxidize an alcohols uses an oxygen atom and produce water: In practice, oxygen atoms are unavailable, so the above equation is only conceptual. Instead, most oxidations use oxides-based reagents, such as metal oxo complexes, sulfoxides, and iodine oxides.

Through a variety of mechanisms, the removal of a hydride equivalent converts a primary or secondary alcohol to an aldehyde or ketone, respectively. The oxidation of primary alcohols to carboxylic acids normally proceeds via the corresponding aldehyde, which is transformed via an aldehyde hydrate (gem-diol, R-CH(OH)2) by reaction with water. Thus, the oxidation of a primary alcohol at the aldehyde level without further oxidation to the carboxylic acid is possible by performing the reaction in absence of water, so that no aldehyde hydrate can be formed.

Ketone and aldehyde formation

Oxidation of alcohols to aldehydes and ketones

Many reagents oxidize secondary alcohols to ketones and primary alcohols to aldehydes. Allylic and benzylic alcohols represent special cases. Aldehydes are susceptible to over oxidation to carboxylic acids.

Chromium(VI) reagents

Alcohol oxidation to carbonyls.svg

Chromiium(VI) reagents are commonly used for these oxidations. One family of Cr(VI) reagents employs the complex CrO3(pyridine)2.[2]

  • Sarett's reagent: a solution of CrO3(pyridine)2 in pyridine. It was popularized for selective oxidation of primary and secondary alcohols to carbonyl compounds.
  • Collins reagent is a solution of the same CrO3(pyridine)2 but in dichloromethane. The Ratcliffe variant of Collins reagent relates to details of the preparation of this solution, i.e., the addition of chromium trioxide to a solution of pyridine in methylene chloride.[3]

A second family of Cr(VI) reagents are salts, featuring the pyridinium cation (C5H5NH+).

  • pyridinium dichromate (PDC) is the pyridium salt of dichromate, [Cr2O7]2-.
  • pyridinium chlorochromate (PCC) is the pyridinium salt of [CrO3Cl]−.

These salts are less reactive, more easily handled, and more selective than Collins reagent in oxidations of alcohols.

The above reagents represent improvements over the older Jones reagent, a solution of chromium trioxide in aqueous sulfuric acid.

Dess–Martin and related oxidations

The Dess–Martin periodinane is a mild oxidant for the conversion of alcohols to aldehydes or ketones.[4] The reaction is performed under standard conditions, at room temperature, most often in dichloromethane. The reaction takes between half an hour and two hours to complete. The product is then separated from the spent periodinane.[5] Many iodosyl-based oxidants have been developed, e.g. IBX.

Swern oxidation

Swern oxidation uses oxalyl chloride, dimethylsulfoxide, and an organic base, such as triethylamine.

Swern Oxidation Scheme.png

The by-products are dimethyl sulfide (Me2S), carbon monoxide (CO), carbon dioxide (CO2) and – when triethylamine is used as base – triethylammonium chloride (C6H15NHCl).

Oppenauer oxidation

Main page: Chemistry:Oppenauer oxidation
Oppenauer.png

This seldom-used method interconverts alcohols and carbonyls.

Niche methods

Ley oxidation uses NMO as the stoichiometric oxidant with tetrapropylammonium perruthenate as a catalyst.

Fétizon oxidation, also a seldom-used method, uses silver carbonate supported on Celite. This reagent operates through single electron oxidation by the silver cations.

Fetizon's reagent mechanism.jpg

Another method is the oxoammonium-catalyzed oxidation.

Additionally, sodium hypochlorite (or household bleach) in acetone has been reported for efficient conversion of secondary alcohols in the presence of primary alcohols (Stevens oxidation).[6]

soluble transition metal complexes catalyze the oxidation of alcohols by presence of dioxygen or another terminal oxidant.[7]

Oxidation of diols

Oxidative cleavage of carbon-carbon bond in 1,2-diols

Compounds possessing two hydroxy groups located on adjacent carbons —that is, vicinal diols/ 1,2-diols — suffer oxidative breakage at a carbon-carbon bond with some oxidants such as sodium periodate (NaIO4), (diacetoxyiodo)benzene (PhI(OAc)2)[8] or lead tetraacetate (Pb(OAc)4), resulting in generation of two carbonyl groups. The reaction is also known as glycol cleavage.

Oxidation of primary alcohols to carboxylic acids

Alcohol to acid (cropped).png

When a primary alcohol is converted to a carboxylic acid, the terminal carbon atom increases its oxidation state by four. The direct oxidation of primary alcohols to carboxylic acids can be carried out using a variety of reagents.

Aldehydes are readily oxidized using Cr(VI) and Mn(VII) reagents to carboxylic acids.

Potassium permanganate

Potassium permanganate (KMnO4) oxidizes primary alcohols to carboxylic acids very efficiently. This reaction, which was first described in detail by Fournier,[9][10] is typically carried out by adding KMnO4 to a solution or suspension of the alcohol in an alkaline aqueous solution. For the reaction to proceed efficiently, the alcohol must be at least partially dissolved in the aqueous solution. This can be facilitated by the addition of an organic co-solvent such as dioxane, pyridine, acetone or t-BuOH. KMnO4 reacts with many functional groups, such as secondary alcohols, 1,2-diols, aldehydes, alkenes, oximes, sulfides and thiols, and carbon-carbon double bonds. Thus, selectivity is an issue.

Ciufolini and Swaminathan [11] oxidized a primary alcohol to carboxylic acid with KMnO4 in aqueous NaOH during the obtention of a rare amino acid derivative needed for the preparation of antibiotics isolated from Actinomadura luzonensis, a microorganism found in a soil sample collected in Luzon island in the Philippines

Jones oxidation

Main page: Chemistry:Jones oxidation

The so-called Jones reagent, prepared from chromium trioxide (CrO3) and aqueous sulfuric acid, oxidizes alcohols to a carboxylic acid. The protocol frequently affords substantial amounts of esters.[12] Problems are the toxicity and environmental unfriendliness of the reagent. Catalytic variant, involving treatment with excess of periodic acid (H5IO6) have been described.[13]

Crimmins and DeBaillie[14]

Two-step oxidation of alcohols to acids via isolated aldehydes

As a lot of the aforementioned conditions for the oxidations of primary alcohols to acids are harsh and not compatible with common protection groups, organic chemists often use a two-step procedure for the oxidation to acids. The alcohol is oxidized to an aldehyde using one of the many procedures above. This sequence is often used in natural product synthesis as in their synthesis of platencin.[15]

Niche methods and reagents

Ruthenium tetroxide is an aggressive, seldom-used agent that allows mild reaction conditions.

Heyns oxidation.[16]

The use of chlorites as terminal oxidants in conjunction with both hypochlorites and TEMPO gives carboxylic acids without chlorination side products.[17] The reaction is usually carried out in two steps in the same pot: partial oxidation is effected with TEMPO and hypochlorite, then chlorite is added to complete the oxidation. Only primary alcohol oxidation is observed. In conjunction with Sharpless dihydroxylation, this method can be used to generate enantiopure α-hydroxy acids.[18]

The Pinnick oxidation uses sodium chlorite.[19]

References

  1. ↑ Burton, George et al. (2000). Salters Advanced Chemistry: Chemical (2nd ed.). Heinemann. ISBN:0-435-63120-9
  2. ↑ "Chromium-based Reagents". Oxidation of Alcohols to Aldehydes and Ketones. Basic Reactions in Organic Synthesis. 2006. pp. 1–95. doi:10.1007/0-387-25725-X_1. ISBN 0-387-23607-4. 
  3. ↑ J. C. Collins, W.W. Hess (1972). "Aldehydes from Primary Alcohols by Oxidation with Chromium Trioxide: Heptanal". Organic Syntheses 52: 5. doi:10.15227/orgsyn.052.0005. 
  4. ↑ Dess, D. B.; Martin, J. C. J. Am. Chem. Soc. 1991, 113, 7277–87.
  5. ↑ J. S. Yadav, et al. "Recyclable 2nd generation ionic liquids as green solvents for the oxidation of alcohols with hypervalent iodine reagents", Tetrahedron, 2004, 60, 2131–35
  6. ↑ "Convenient and inexpensive procedure for oxidation of secondary alcohols to ketones". Journal of Organic Chemistry 45 (10): 2030–2032. 1980. doi:10.1021/jo01298a066. 
  7. ↑ Parmeggiani, Camilla; Cardona, Francesca (2012-01-03). "Transition metal based catalysts in the aerobic oxidation of alcohols" (in en). Green Chemistry 14 (3): 547–564. doi:10.1039/C2GC16344F. ISSN 1463-9270. https://pubs.rsc.org/en/content/articlelanding/2012/gc/c2gc16344f. 
  8. ↑ "An expedient procedure for the oxidative cleavage of olefinic bonds with PhI(OAc)2, NMO, and catalytic OsO4". Organic Letters 12 (7): 1552–5. April 2010. doi:10.1021/ol100290a. PMID 20192259. 
  9. ↑ Fournier, H.M. (1907). "Transformation des alcools primaires saturès en acides monobasiques correspondants". C. R. Acad. Sci.: 331. 
  10. ↑ Fournier, H.M. (20 July 1909). "Sur la préparation des acides gras et de leurs anhydres". Bull. Soc. Chim. Fr.: 920. https://gallica.bnf.fr/ark:/12148/bpt6k5510407r/f1114.item. 
  11. ↑ Ciufolini, M.A.; Swaminathan, S. (1989). "Synthesis of a model depsipeptide segment of Luzopeptins (BBM 928), potent antitumor and antiretroviral antibiotics". Tetrahedron Lett. 30 (23): 3027. doi:10.1016/S0040-4039(00)99393-6. 
  12. ↑ "Chromium-based Reagents". Oxidation of Alcohols to Aldehydes and Ketones. Basic Reactions in Organic Synthesis. 2006. pp. 1–95. doi:10.1007/0-387-25725-X_1. ISBN 0-387-23607-4. 
  13. ↑ Song, Z.J.; Zhao, M.; Desmond, R.; Devine, P.; Tschaen, D.M.; Tillyer, R.; Frey, L.; Heid, R. et al. (1999). "Practical Asymmetric Synthesis of an Endothelin Receptor Antagonist". J. Org. Chem. 64 (26): 9658. doi:10.1021/jo991292t. 
  14. ↑ Crimmins, M.T.; DeBaillie, A.C. (2006). "Enantioselective Total Synthesis of Bistramide A". J. Am. Chem. Soc. 128 (15): 4936–7. doi:10.1021/ja057686l. PMID 16608311. 
  15. ↑ Nicolaou K.C.; Scott Tria G.; Edmonds D. J. (2008). "Total Synthesis of Platencin". Angew. Chem. 120 (9): 1804. doi:10.1002/ange.200800066. 
  16. ↑ Marcos Fernández; Gabriel Tojo (2006). Oxidation of Primary Alcohols to Carboxylic Acids: A Guide to Current Common Practice (Basic Reactions in Organic Synthesis). Berlin: Springer. ISBN 0-387-35431-X. 
  17. ↑ Song, Z. J.; Zhao, M.; Desmond, R.; Devine, P.; Tschaen, D. M.; Tillyer, R.; Frey, L.; Heid, R.; Xu, F.; Foster, B.; Li, J.; Reamer, R.; Volante, R.; Grabowski, E. J. J.; Dolling, U. H.; Reider, P. J.; Okada, S.; Kato, Y.; Mano, E. J. Org. Chem. 1999, 64, 9658.
  18. ↑ Sharpless, K. B.; Amberg, W.; Bennani, Y. L.; Crispino, G. A.; Hartung, J.; Jeong, K. S.; Kwong, H. L.; Morikawa, K.; Wang, Z. M.; Xu, D.; Zhang, X. L. J. Org. Chem. 1992, 57, 2768.
  19. ↑ Bal B.S.; Childers, Jr. W.E.; Pinnick H.W. (1981). "Oxidation of α,β-unsaturated aldehydes". Tetrahedron 37 (11): 2091. doi:10.1016/S0040-4020(01)97963-3. 



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