Oxidation Adjacent to CC Bonds

Page, Philip C. Bulman; McCarthy, Timothy J.

doi:10.1016/b978-0-08-052349-1.00184-0

Cited by 38 publications

(19 citation statements)

References 277 publications

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“…Inspired by nature, chemists have developed enantioselective dihydroxylations, epoxidations, and other oxidations of unsaturated hydrocarbons. More recently, the catalytic enantioselective allylic C–H oxidation of alkenes has emerged as a powerful chemical strategy, streamlining the production of pharmaceuticals, natural products, fine chemicals and other functional materials 4–7 . Allylic functionalization provides a direct path to chiral synthons with a newly formed stereocenter from petrochemical feedstocks while preserving the olefin functionality as a handle for further elaboration.…”

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Catalytic allylic oxidation of internal alkenes to a multifunctional chiral building block

Bayeh

Tambar

2017

Nature

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The stereoselective oxidation of hydrocarbons represents one of the most significant advances in synthetic chemistry over the last fifty years1–3. Inspired by nature, chemists have developed enantioselective dihydroxylations, epoxidations, and other oxidations of unsaturated hydrocarbons. More recently, the catalytic enantioselective allylic C–H oxidation of alkenes has emerged as a powerful chemical strategy, streamlining the production of pharmaceuticals, natural products, fine chemicals and other functional materials4–7. Allylic functionalization provides a direct path to chiral synthons with a newly formed stereocenter from petrochemical feedstocks while preserving the olefin functionality as a handle for further elaboration. Various metal-based catalysts have been discovered for the enantioselective allylic C–H oxidation of simple alkenes with cyclic or terminal double bonds8–16. However, a general and selective allylic oxidation remains elusive with the more common internal alkenes. Here, we report the enantioselective, regioselective, and E/Z selective allylic oxidation of unactivated internal alkenes via a catalytic asymmetric hetero-ene reaction with a chalcogen-based oxidant. This method represents the first example of selectively converting unsymmetrical internal alkenes into allylic functionalized products with high stereoselectivity and regioselectivity. Stereospecific transformations of the multifunctional allylic oxidation products highlight the potential for rapidly converting internal alkenes into a broad range of enantioenriched structures that can be utilized in the synthesis of complex target molecules.

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Catalytic allylic oxidation of internal alkenes to a multifunctional chiral building block

Bayeh

Tambar

2017

Nature

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“…Selenium dioxide is commonly used to oxidize the α-methylene carbon atoms adjacent to a double bond to form allylic hydroxy derivatives (1). One serious complication of this reaction is the difficulty of removing the colloidal reduced forms of selenium after the reaction.…”

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“…Aldehydes, ketones, and carboxylic esters also can be subjected to α-oxidation by selenium dioxide (10). Allylic rearrangement reactions often are found to accompany this type of reaction, and cis double bonds tend to isomerize to the trans configuration (1,2). While allylic hydroxylation reactions involving olefinic compounds have been extensively documented in the chemical literature, comparatively little is reported on the oxidation of acetylenic fatty acids by selenium dioxide/TBHP.…”

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Oxidation reactions of acetylenic fatty esters with selenium dioxide/tert‐butyl hydroperoxide

Jie

Pasha

Alam

1997

Lipids

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Reaction of methyl undec-10-ynoate (1) with selenium dioxide/tert-butyl hydroperoxide (TBHP) in aqueous dioxane gave methyl 9-oxo-undec-10-ynoate (2, 9%) and 9-hydroxy-undec-10-ynoate (3, 60%), while methyl octadec-9-ynoate (4) yielded mixtures of positional isomers of mono-keto (viz. methyl 8-oxo- and 11-oxo-octadec-9-ynoate, 5, 5%), hydroxy-keto (viz. methyl 8-hydroxy-11-oxo- and 11-hydroxy-8-oxo-octadec-9-ynoate, 6, 10%), and dihydroxy (viz. methyl 8,11-dihydroxy-octadec-9-ynoate, 7, 24%) derivatives. Similar treatment of a conjugated diacetylenic fatty ester (methyl octadeca-6,8-diynoate, 8) furnished a mixture of methyl 5-oxo- and 10-oxo-octadeca-6,8-diynoate (9, 12%) and a complex mixture of very polar products. Reaction of methyl octadec-11E-en-9-ynoate (methyl santalbate) (10) with selenium dioxide/TBHP in aqueous dioxane gave exclusively a mixture of regiospecific products, viz. methyl 8-oxo-octadec-11(E)Z-en-9-ynoate (11, 6%) and methyl 8-hydroxy-octadec-11E-en-9-ynoate (12, 70%). The structures of the various products were determined by a combination of spectroscopic and mass spectral analyses.

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“…[3,4] An oxidation reaction of special interest is the allylic oxidation that allows the conversion of alkenes into allyl alcohols or enones. [5] Allylic oxidations via the direct sp 3 C-H bond activation of alkenes and alkylarenes to the corresponding α, β-unsaturated enones and carbonyl compounds are important transformations with a wide variety of industrial applications [6,7] including the synthesis of drug precursors and building blocks in many organic syntheses.…”

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Visible Light Promoted Allylic C–H Oxidation

Srivastava¹,

Singh

Singh³

2017

Croat. Chem. Acta

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A mild and efficient one-pot visible light-induced method has been developed for the allylic oxidation. The oxidation of allylic systems has played a prominent role in this context as possibly the most widely applied C-H functionalization, owing to the utility of enones. The allylic C-H oxidation is relatively simple and predictable, even on a preparative scale, because active species generated at the allylic position are stabilized by the double bond.

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Oxidation Adjacent to CC Bonds

Cited by 38 publications

References 277 publications

Catalytic allylic oxidation of internal alkenes to a multifunctional chiral building block

Catalytic allylic oxidation of internal alkenes to a multifunctional chiral building block

Oxidation reactions of acetylenic fatty esters with selenium dioxide/tert‐butyl hydroperoxide

Visible Light Promoted Allylic C–H Oxidation

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