ArticleAngewandte Chemie (International ed. in English)2021
Origins of Endo Selectivity in Diels-Alder Reactions of Cyclic Allene Dienophiles.
Article in Angewandte Chemie (International ed. in English), 2021. The graph could read no effect estimate from its abstract, so it casts no vote on the map. Cited by 24 papers.
What it found
Each row is one number read from the abstract, on the scale the paper reported it, with its interval. Left of the dashed line favours the treatment, right favours the comparator. Under each row is the sentence it came from. New to these charts? A ten-minute tutorial.
The abstract states no effect estimate the extractor could read, or names no intervention and outcome on the map, so this paper lights no cell and moves no belief. It is still indexed, cited and linked below.
The trial behind it
Trials whose registry record cites this paper, or whose number appears in the abstract. A trial that started after this paper was published is citing it as background, not reporting it.
Neither the registry nor the abstract names a trial number. If this is a trial report, that itself is worth knowing.
Who cites it
24 citing papers in PubMed.
- Diradical Character of Cyclic Allenes Enables Their Thermal (2 + 2) Cycloadditions.Journal of the American Chemical Society · 2026Article
- Seven-Membered Azacyclic Allenes: Synthesis, Trapping, and Stereochemical Transfer Studies.Journal of the American Chemical Society · 2026Article
- Mechanisms of Kobayashi eliminations for the generation of highly strained arynes, cyclic cumulenes, and anti-Bredt olefins.Chemical science · 2025Article
- Woodward and Hoffmann on Secondary Orbital Interactions. How to Make a Fine Two-Course Meal from Leftovers.Chemical record (New York, N.Y.) · 2025Review
- Substantial Magnetic Fields Arising from Ballistic Ring Currents in Single-Molecule Junctions.JACS Au · 2025Article
- Development of a Vinylated Cyclic Allene: A Fleeting Strained Diene for the Diels-Alder Reaction.Angewandte Chemie (International ed. in English) · 2025Article
- Computational Investigation of a COACS omega · 2025Article
- Geometric distortion as an enabling tool for organic synthesis.Nature synthesis · 2025Article
- Total Synthesis of Lissodendoric Acid A.Angewandte Chemie (International ed. in English) · 2024Article
- Diels-Alder Cycloadditions of Oxacyclic Allenes and α-Pyrones.Organic letters · 2024Article
- Access to Complex Scaffolds Through [2 + 2] Cycloadditions of Strained Cyclic Allenes.Journal of the American Chemical Society · 2024Article
- Computational Organic Chemistry: The Frontier for Understanding and Designing Bioorthogonal Cycloadditions.Topics in current chemistry (Cham) · 2024Review
- Chiral Jahn-Teller Distortion in Quasi-Planar Boron Clusters.Molecules (Basel, Switzerland) · 2024Article
- Generation and reactivity of unsymmetrical strained heterocyclic allenes.Nature synthesis · 2024Article
- Understanding Current Density in Molecules Using Molecular Orbitals.The journal of physical chemistry. A · 2023Article
- Cyclic Allene Approach to the Manzamine Alkaloid Keramaphidin B.Organic letters · 2023Article
- Catalyst-Controlled Annulations of Strained Cyclic Allenes with π-Allylpalladium Complexes.Journal of the American Chemical Society · 2023Article
- A Distinct Mode of Strain-Driven Cyclic Allene Reactivity: Group Migration to the Central Allene Carbon Atom.Journal of the American Chemical Society · 2023Article
- How Bases Catalyze Diels-Alder Reactions.Chemistry (Weinheim an der Bergstrasse, Germany) · 2023Article
- Total synthesis of lissodendoric acid A via stereospecific trapping of a strained cyclic allene.Science (New York, N.Y.) · 2023Article
Corrections and comments
PubMed lists nothing against this paper. Absence here is not a guarantee, only a check that was made.
Authors and funding
5 authors.
Funding
Abstract
Strained cyclic allenes, first discovered in 1966 by Wittig and co-workers, have recently emerged as valuable synthetic building blocks. Previous experimental investigations, and computations reported here, demonstrate that the Diels-Alder reactions of furans and pyrroles with 1,2-cyclohexadiene and oxa- and azaheterocyclic analogs proceed with endo selectivity. This endo selectivity gives the adduct with the allylic saturated carbon of the cyclic allene endo to the diene carbons. The selectivity is very general and useful in synthetic applications. Our computational study establishes the origins of this endo selectivity. We analyze the helical frontier molecular orbitals of strained cyclic allenes and show how secondary orbital and electrostatic effects influence stereoselectivity. The LUMO of carbon-3 of the allene (C-3 is not involved in primary orbital interactions) interacts in a stabilizing fashion with the HOMO of the diene in such a way that the carbon of the cyclic allene attached to C-1 favors the endo position in the transition state. The furan LUMO, allene HOMO interaction reinforces this preference. These mechanistic studies are expected to prompt the further use of long-avoided strained cyclic allenes in chemical synthesis.
Indexed as
Identifiers
What OpenQuestion holds
Registered trials
Read under generation 80e0d062 · epoch 390. Bibliography from PubMed, PubMed Central and OpenAlex; grants from NIH RePORTER; trial links from ClinicalTrials.gov; estimates, votes and beliefs from the OpenQuestion graph.