2-Methoxypropene

Whitaker, K. Sinclair; Whitaker, D. Todd

doi:10.1002/047084289x.rm124

Encyclopedia of Reagents for Organic Synthesis 2001

DOI: 10.1002/047084289x.rm124

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2-Methoxypropene

K. Sinclair Whitaker

D. Todd Whitaker²

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Cited by 2 publications

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“…1 H NMR experiments also revealed no visible interaction between the HE and TMSCl in the ground state. When compared to para -toluenepyridinium sulfonate (PPTS), a Brønsted acid used in alcohol protections using 2-methoxypropene, these protic intermediates are comparably acidic. Despite this, the reaction does not proceed in the absence of any additive.…”

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α-Tertiary Dialkyl Ether Synthesis via Reductive Photocatalytic α-Functionalization of Alkyl Enol Ethers

et al. 2020

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The photocatalytic construction of C(sp 3)-rich α-tertiary dialkyl ethers through the reductive αfunctionalization of alkyl enol ether substrates with conjugated alkenes in the presence of a Hantzsch ester terminal reductant under blue LED irradiation, is described. Pivoting on oxocarbenium ion generation via an initial TMSClfacilitated protic activation of the enol ether substrate, subsequent single electron transfer delivers the key nucleophilic αoxy tertiary radical capable of productively combining with a variety of alkene substrates. The new reductive functionalization strategy was simple to perform, efficient, broad in scope with respect to both alkene acceptor and enol ether donor fragments and delivered a wide range of complex α-tertiary dialkyl ether architectures. Scheme 4. Proposed mechanism for the photocatalytic α-functionalization of enol ethers Single electron transfer from the iridium(II) species (E°1/2 =-1.37 V) to the oxocarbenium ion (E°1/2 (calc) =-1.12 V) gives rise to the nucleophilic α-oxy radical 31 which then undergoes Giese-type addition with the conjugated alkene to produce the γ-amino radical. Subsequent intramolecular HAT and then intermolecular HAT permits termination, delivering the α-tertiary dialkyl ether 3a. This HAT can take place from either HE radical cation (shown, Scheme 4, right), or HEH•, rendering either HP+ or HE radical cation as the potential respective proton sources for the corresponding mechanisms (see ESI for more details). Aligned to previous investigations, the pathway shown is most likely in operation. 32 In conclusion, a mild photocatalytic reductive αfunctionalization of alkyl enol ethers has been developed. Through Lewis acid-assisted protic activation of the enol ether to generate the corresponding oxocarbenium ion and subsequent single electron reduction, we have identified a new approach to access the α-oxy dialkyl radical. This reactive intermediate was shown to engage in Giesetype coupling reactions with a wide range of alkene substrates to deliver 33 examples of α-tertiary dialkyl ether architectures. Work to understand the source of the acidity and applying this concept to further reaction systems is currently underway.

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α-Tertiary Dialkyl Ether Synthesis via Reductive Photocatalytic α-Functionalization of Alkyl Enol Ethers

et al. 2020

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Atmospheric insight into the reaction mechanism and kinetics of isopropenyl methyl ether (i-PME) initiated by OH radicals and subsequent oxidation of product radicals

Baruah

Deka

Gour

et al. 2021

Environ Sci Pollut Res

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2-Methoxypropene

Cited by 2 publications

References 44 publications

α-Tertiary Dialkyl Ether Synthesis via Reductive Photocatalytic α-Functionalization of Alkyl Enol Ethers

α-Tertiary Dialkyl Ether Synthesis via Reductive Photocatalytic α-Functionalization of Alkyl Enol Ethers

Atmospheric insight into the reaction mechanism and kinetics of isopropenyl methyl ether (i-PME) initiated by OH radicals and subsequent oxidation of product radicals

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