A new umpolung for direct γ-regioselective nucleophilic addition of alcohols to γ-enolizable α,β-unsaturated aldehydes

Arimitsu, Satoru; Mari, Oshiro; Yonamine, Tsunaki

doi:10.1016/j.tetlet.2017.05.058

Cited by 2 publications

(2 citation statements)

References 25 publications

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“…A nucleophilic addition of alcohols to γ-enolizable α,β-unsaturated aldehydes in an umpolung fashion using MeSO 3 H, chloranil as an oxidant in 1:1 MeCN/HFIP was reported (Scheme ). MeCN and HFIP alone as well as other solvents like THF, DMF, toluene, DCM, MeNO 2 , and EtOAc led to diminished yields. HFIP was proposed to accelerate this reaction via stabilization of the allylic cation intermediate.…”

Section: Oxidations and Reductionsmentioning

confidence: 99%

HFIP in Organic Synthesis

et al. 2022

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1,1,1,3,3,3-Hexafluoroisopropanol (HFIP) is a polar, strongly hydrogen bond-donating solvent that has found numerous uses in organic synthesis due to its ability to stabilize ionic species, transfer protons, and engage in a range of other intermolecular interactions. The use of this solvent has exponentially increased in the past decade and has become a solvent of choice in some areas, such as C–H functionalization chemistry. In this review, following a brief history of HFIP in organic synthesis and an overview of its physical properties, literature examples of organic reactions using HFIP as a solvent or an additive are presented, emphasizing the effect of solvent of each reaction.

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Section: Oxidations and Reductionsmentioning

confidence: 99%

HFIP in Organic Synthesis

et al. 2022

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“…Recently, the selective hydrogenation of α, β-unsaturated aldehydes to produce corresponding unsaturated alcohols has attracted wide attention, because these unsaturated alcohols can be employed to produce valuable ne chemical and pharmaceutical intermediates and products [1,2,3,4,5,6]. α, βunsaturated aldehydes contain C=C bonds and C=O bonds.…”

Section: Introductionmentioning

confidence: 99%

Comparative DFT study on selective hydrogenation of acrolein catalyzed by pure Mo2C(001) and Pt/Mo2C(001)

Wu¹,

Huang²,

Wang³

et al. 2021

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In this paper, Density Functional Theory (DFT) calculations were conducted to study the adsorption and stepwise hydrogenation of acrolein (CH 2 =CHCH=O) on pure Mo 2 C(001) and Pt/Mo 2 C(001). The electronic properties were investigated by Mulliken population analysis. The results showed that Mo atoms obtained some electrons from surrounding Pt and C atoms, thereby enhancing the hydrogenation activity of Mo atoms around Pt atoms and forming local active sites dominated by Mo atoms around Pt atoms. As a result, the adsorption energy of the species on Pt/Mo 2 C(001) is generally higher than that on Mo 2 C(001), and the activation energies of the elementary reactions involved in stepwise hydrogenation of acrolein on Pt/Mo 2 C(001) are lower than those on Mo 2 C(001). Moreover, Pt/Mo 2 C(001) exhibits higher selectivity for C=O bond hydrogenation than Mo 2 C(001) and produces more allyl alcohol.

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A new umpolung for direct γ-regioselective nucleophilic addition of alcohols to γ-enolizable α,β-unsaturated aldehydes

Cited by 2 publications

References 25 publications

HFIP in Organic Synthesis

HFIP in Organic Synthesis

Comparative DFT study on selective hydrogenation of acrolein catalyzed by pure Mo2C(001) and Pt/Mo2C(001)

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