Novel Anti‐Markovnikov Regioselectivity in the Wacker Reaction of Styrenes

Wright, Joseph A.; Gaunt, Matthew J.; Spencer, Jonathan B.

doi:10.1002/chem.200400644

Cited by 102 publications

(68 citation statements)

References 43 publications

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“…The solvent was removed at reduced pressure to give the 2.9 g (89 %) of 5 as a white solid. The NMR spectra of 5 are in accordance with the literature data . CH 2 Cl 2 (10 mL) and 40 % aqueous Na 2 S 2 O 5 (50 mL) was added and the mixture was stirred for 20 min.…”

Section: Methodssupporting

confidence: 69%

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Aerobic Aliphatic Hydroxylation Reactions by Copper Complexes: A Simple Clip‐and‐Cleave Concept

Becker

Zhyhadlo

Butova

et al. 2018

Chemistry A European J

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A simple imine clip-and-cleave concept has been developed for the selective hydroxylation of non-activated CH bonds in aliphatic aldehydes with dioxygen through a copper complex. The synthetic protocol involves reaction of a substrate aldehyde with N,N-diethyl-ethylendiamine to give the corresponding imine, which is used as a bidentate donor ligand forming a copper(I) complex with [Cu(CH CN) ][CF SO ]. After exposure of the reaction mixture to dioxygen acidic cleavage and aqueous workup liberates the corresponding β-hydroxylated aldehyde. The concept for the hydroxylation of trimethylacetaldehyde as well as adamantane and diamantane 1-carbaldehydes was investigated and the corresponding β-hydroxy aldehydes were obtained with high selectivities. The results of low temperature stopped-flow measurements indicate the formation of a bis(μ-oxido)dicopper complex as reactive intermediate. According to density functional theory (DFT, RI-BLYP-D3/def2-TZVP(SDD)/ COSMO(CH Cl )//RI-PBE-D3/def2-TZVP(SDD)) computations CH bonds suitably predisposed to the [Cu O ] core undergo hydroxylation in a concerted step with particularly low activation barriers, which explains the experimentally observed regioselectivities.

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Section: Methodssupporting

confidence: 69%

“…The NMR spectra of 5 are in accordance with the literature data. [36] CH 2 Cl 2 (10 mL) and 40 %a queous Na 2 S 2 O 5 (50 mL) was added and the mixture was stirred for 20 min. The thus formed precipitate was filtered, washed with dimethyl ether (20 mL) and dried in vacuum to give air-stable bisulfite derivative of 5.…”

Section: Computational Detailsmentioning

confidence: 99%

Aerobic Aliphatic Hydroxylation Reactions by Copper Complexes: A Simple Clip‐and‐Cleave Concept

Becker

Zhyhadlo

Butova

et al. 2018

Chemistry A European J

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“…[39] The extent of AM selectivity for several substrates indicate the possible involvement of an h 4 -palladium-styrene complex. The AM oxidation of 1,5-dienes has been reported by Ho and co-workers under Wacker oxidation conditions, [40] although substoichiometric amounts of palladium(II) and gem disubstitution were required for AM-selective oxidation of this substrate class.…”

Section: Mechanistic Studiesmentioning

confidence: 99%

Palladium‐Catalyzed anti‐Markovnikov Oxidation of Terminal Alkenes

2014

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The palladium-catalyzed oxidation of alkenes, the Wacker-Tsuji reaction, is undoubtedly a classic in organic synthesis and provides reliable access to methyl ketones from terminal alkenes under mild reaction conditions. Methods that switch the selectivity of the reaction to provide the aldehyde product are desirable because of the access they provide to a valuable functional group, however such methods are elusive. Herein we survey both the methods which have been developed recently in achieving such selectivity and discuss common features and mechanistic insight which offers promise in achieving the goal of a general method for anti-Markovnikov-selective olefin oxidations.

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“…The experimental result is unexpected since the oxidation of aliphatic olefins to aldehydes is difficult and only aromatic alkenes were reported to be oxidized in many references. 19,48 Some internal alkenes cyclohexene and trans-4-octene were employed as substrates. Unfortunately, the oxidation reaction did not occur (Table 3, entries 13 and 14).…”

Section: Oxidative Cleavage Reaction Of Various Olefinsmentioning

confidence: 99%

Selective oxidative cleavage of terminal olefins into aldehydes catalyzed by copper(ii) complex

et al. 2015

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ARTICLE This journal isA simple method for oxidative C=C bond cleavage of terminal olefins to aldehydes with H 2 O 2 catalyzed by copper(II) complex LCu consisted of copper(II) and macrocyclic ligand 5,7,12,14-tetramethyl-1,4,8,11-tetraazacyclotetradeca-4,7,11,14-tetraene (L) was described. This study indicated that the copper(II) complex displayed excellent catalytic ability for the selective oxidation of terminal olefins to aldehydes with high selectivity (S>90%) in CH 3 CN at 30 ℃ . The possible catalytic reaction mechanism of oxidation of terminal olefins was discussed.

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Novel Anti‐Markovnikov Regioselectivity in the Wacker Reaction of Styrenes

Cited by 102 publications

References 43 publications

Aerobic Aliphatic Hydroxylation Reactions by Copper Complexes: A Simple Clip‐and‐Cleave Concept

Aerobic Aliphatic Hydroxylation Reactions by Copper Complexes: A Simple Clip‐and‐Cleave Concept

Palladium‐Catalyzed anti‐Markovnikov Oxidation of Terminal Alkenes

Selective oxidative cleavage of terminal olefins into aldehydes catalyzed by copper(ii) complex

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