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

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...

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Bibliographic Details
Published in:Nature communications 2023-06, Vol.14 (1), p.3511-3511, Article 3511
Main Authors: Zeng, Lei, Liu, Shihan, Lan, Yu, Gao, Lizhu
Format: Article
Language:English
Subjects:
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140/131
140/58
639/638/403/935
639/638/549/972
639/638/77/883
Acids
Acrolein
Activated carbon
Aldehydes
Alkenes
Asymmetry
Boron
Carbonyl compounds
Carbonyls
Diels-Alder reactions
Humanities and Social Sciences
Ketones
Laboratories
multidisciplinary
Natural products
Ring structures
Science
Science (multidisciplinary)
Substrates
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Summary: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. The asymmetric inverse-electron-demand oxa-Diels–Alder reaction (IODA) between activated α,β-unsaturated carbonyl compounds with highly polarized alkenes has been reported before but acroleins or simple alkenes were so-far rarely employed as substrates. Here, the authors study the catalytic asymmetric intermolecular IODA reaction between acroleins and simple alkenes.
ISSN:2041-1723
2041-1723
DOI:10.1038/s41467-023-39184-z