Copper‐Catalyzed Reduction of Alkyl Triflates and Iodides: An Efficient Method for the Deoxygenation of Primary and Secondary Alcohols

Dang, Hester; Cox, Nick; Lalić, Gojko

doi:10.1002/ange.201307697

Cited by 5 publications

(1 citation statement)

References 66 publications

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“…9 ) which is inconsistent with reaction at room temperature. Experimental results described above also indicate that TEMPO inhibits the reaction, which is further inconsistent with a copper hydride pathway 57 .…”

Section: Resultsmentioning

confidence: 91%

Autocatalytic photoredox Chan-Lam coupling of free diaryl sulfoximines with arylboronic acids

et al. 2021

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N-Arylation of NH-sulfoximines represents an appealing approach to access N-aryl sulfoximines, but has not been successfully applied to NH-diaryl sulfoximines. Herein, a copper-catalyzed photoredox dehydrogenative Chan-Lam coupling of free diaryl sulfoximines and arylboronic acids is described. This neutral and ligand-free coupling is initiated by ambient light-induced copper-catalyzed single-electron reduction of NH-sulfoximines. This electron transfer route circumvents the sacrificial oxidant employed in traditional Chan-Lam coupling reactions, increasing the environmental friendliness of this process. Instead, dihydrogen gas forms as a byproduct of this reaction. Mechanistic investigations also reveal a unique autocatalysis process. The C–N coupling products, N-arylated sulfoximines, serve as ligands along with NH-sulfoximine to bind to the copper species, generating the photocatalyst. DFT calculations reveal that both the NH-sulfoximine substrate and the N-aryl product can ligate the copper accounting for the observed autocatalysis. Two energetically viable stepwise pathways were located wherein the copper facilitates hydrogen atom abstraction from the NH-sulfoximine and the ethanol solvent to produce dihydrogen. The protocol described herein represents an appealing alternative strategy to the classic oxidative Chan-Lam reaction, allowing greater substrate generality as well as the elimination of byproduct formation from oxidants.

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Section: Resultsmentioning

confidence: 91%

Autocatalytic photoredox Chan-Lam coupling of free diaryl sulfoximines with arylboronic acids

et al. 2021

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B(C₆F₅)₃‐katalysierte chemoselektive Defunktionalisierung von etherhaltigen primären Alkyltosylaten mit Hydrosilanen

2017

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Eine durchB (C 6 F 5 ) 3 /Et 3 SiH vermittelte C(sp 3 )-O-Bindungsspaltung verläuft in Gegenwart von primären und sekundären Silylethern und Arylethern bevorzugt mit primären Tosylaten. Dieser Reaktivitätsunterschied ermçglicht die chemoselektive Defunktionalisierung etlicher 1,n-Diole,u nd die selektive Desoxygenierung einer Hydroxymethylgruppe eines orthogonal geschützten Kohlenhydrats veranschaulicht das Potenzial der neuen Reaktionsvorschrift. Tosylate mit einer benachbarten Phenylgruppe werden mit anchimerer Unterstützung gespalten.

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Cu‐Catalyzed Hydroxymethylation of Unactivated Alkyl Iodides with CO To Provide One‐Carbon‐Extended Alcohols

Zhao

Mankad

2018

Angewandte Chemie

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We have developed ar eductive carbonylation method by which unactivated alkyli odides can be hydroxymethylated to provideo ne-carbon-extended alcohol products under Cu-catalyzed conditions.The method is tolerant of alkyl b-hydrogen atoms,i sr obust towards aw ide variety of functional groups,a nd was applied to primary,s econdary,a nd tertiary alkyli odide substrates.M echanistic experiments indicate that the transformation proceeds by atom-transfer carbonylation (ATC) of the alkyli odide followed in tandem by two CuH-mediated reductions in rapid succession. This radical mechanism renders the Cu-catalyzed system complementary to precious-metal-catalyzed reductive carbonylation reactions.

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Copper‐Catalyzed Reduction of Alkyl Triflates and Iodides: An Efficient Method for the Deoxygenation of Primary and Secondary Alcohols

Cited by 5 publications

References 66 publications

Autocatalytic photoredox Chan-Lam coupling of free diaryl sulfoximines with arylboronic acids

Autocatalytic photoredox Chan-Lam coupling of free diaryl sulfoximines with arylboronic acids

B(C₆F₅)₃‐katalysierte chemoselektive Defunktionalisierung von etherhaltigen primären Alkyltosylaten mit Hydrosilanen

Cu‐Catalyzed Hydroxymethylation of Unactivated Alkyl Iodides with CO To Provide One‐Carbon‐Extended Alcohols

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Copper‐Catalyzed Reduction of Alkyl Triflates and Iodides: An Efficient Method for the Deoxygenation of Primary and Secondary Alcohols

Cited by 5 publications

References 66 publications

Autocatalytic photoredox Chan-Lam coupling of free diaryl sulfoximines with arylboronic acids

Autocatalytic photoredox Chan-Lam coupling of free diaryl sulfoximines with arylboronic acids

B(C6F5)3‐katalysierte chemoselektive Defunktionalisierung von etherhaltigen primären Alkyltosylaten mit Hydrosilanen

Cu‐Catalyzed Hydroxymethylation of Unactivated Alkyl Iodides with CO To Provide One‐Carbon‐Extended Alcohols

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Product

Resources

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B(C₆F₅)₃‐katalysierte chemoselektive Defunktionalisierung von etherhaltigen primären Alkyltosylaten mit Hydrosilanen