Catalytic Diastereoselective Hetero-Diels–Alder Reaction of α-Haloacroleins with Alkenes: Construction of 3,4-Dihydropyran

Zeng, Lei; Liu, Qian; Rao, Weidong; Gao, Lizhu

doi:10.1021/acs.orglett.2c00341

Cited by 3 publications

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“…1a. This will be a great challenge, as the reactivity of acroleins and the neutral alkenes was low, and furthermore the potentially competitive ene reaction and the cyclobutanation reaction should be effectively suppressed [54][55][56] .…”

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Catalytic asymmetric oxa-Diels–Alder reaction of acroleins with simple alkenes

et al. 2023

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The catalytic asymmetric inverse-electron-demand oxa-Diels–Alder (IODA) reaction is a highly effective synthetic method for creating enantioenriched six-membered oxygen-containing heterocycles. Despite significant effort in this area, simple α,β-unsaturated aldehydes/ketones and nonpolarized alkenes are seldom utilized as substrates due to their low reactivity and difficulties in achieving enantiocontrol. This report describes an intermolecular asymmetric IODA reaction between α-bromoacroleins and neutral alkenes that is catalyzed by oxazaborolidinium cation 1f. The resulting dihydropyrans are produced in high yields and excellent enantioselectivities over a broad range of substrates. The use of acrolein in the IODA reaction produces 3,4-dihydropyran with an unoccupied C6 position in the ring structure. This unique feature is utilized in the efficient synthesis of (+)-Centrolobine, demonstrating the practical synthetic utility of this reaction. Additionally, the study found that 2,6-trans-tetrahydropyran can undergo efficient epimerization into 2,6-cis-tetrahydropyran under Lewis acidic conditions. This structural core is widespread in natural products.

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Catalytic asymmetric oxa-Diels–Alder reaction of acroleins with simple alkenes

et al. 2023

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“…The outline of the reaction pathway is given in Scheme . (1) Bis(silyl)acetals are generated from CO 2 and phenylsilane via the formation of the Zn–hydride complex, (2) the Knoevenagel condensation of 3 with bis(silyl)acetals or formaldehyde affords highly reactive methylidene compounds 6 , and (3) the inverse-electron-demand oxa-Diels–Alder reaction of 6 with 4 gives dihydropyrans 5 . The processes (2) and (3) are a domino-type reaction.…”

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One-Pot Synthesis of Dihydropyrans via CO₂ Reduction and Domino Knoevenagel/oxa-Diels–Alder Reactions

et al. 2023

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Catalytic CO2 reduction with phenylsilane under solvent-free conditions was linked with the one-pot synthesis of 3,4-dihydropyrans from β-dicarbonyl compounds and styrenes. The synthesis includes three processes: (1) bis(silyl)acetal formation from CO2 and phenylsilane and a domino reaction of (2) Knoevenagel condensation and (3) inverse-electron-demand oxa-Diels–Alder reaction. The first process was catalyzed by a pentanuclear ZnII complex (0.07 mol %) to generate bis(silyl)acetals, which were hydrolyzed into formaldehyde to be used in the second step.

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Six-membered ring systems: With O and/or S atoms

Santos,

Silva

2023

Progress in Heterocyclic Chemistry

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Catalytic Diastereoselective Hetero-Diels–Alder Reaction of α-Haloacroleins with Alkenes: Construction of 3,4-Dihydropyran

Cited by 3 publications

References 37 publications

Catalytic asymmetric oxa-Diels–Alder reaction of acroleins with simple alkenes

Catalytic asymmetric oxa-Diels–Alder reaction of acroleins with simple alkenes

One-Pot Synthesis of Dihydropyrans via CO₂ Reduction and Domino Knoevenagel/oxa-Diels–Alder Reactions

Six-membered ring systems: With O and/or S atoms

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Catalytic Diastereoselective Hetero-Diels–Alder Reaction of α-Haloacroleins with Alkenes: Construction of 3,4-Dihydropyran

Cited by 3 publications

References 37 publications

Catalytic asymmetric oxa-Diels–Alder reaction of acroleins with simple alkenes

Catalytic asymmetric oxa-Diels–Alder reaction of acroleins with simple alkenes

One-Pot Synthesis of Dihydropyrans via CO2 Reduction and Domino Knoevenagel/oxa-Diels–Alder Reactions

Six-membered ring systems: With O and/or S atoms

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One-Pot Synthesis of Dihydropyrans via CO₂ Reduction and Domino Knoevenagel/oxa-Diels–Alder Reactions