Construction of bicyclic tetrahydroisoquinolinones by combination of an IMDAF-ring cleavage reaction of <i>N</i>-allyl-2-furan-2-yl-acetamides
Bibliographic record
Abstract
The intramolecular Diels-Alder reaction of furanyl amides derived from 2-furylacetic acid has been examined. Substrates containing either an imide or tertiary amide linkage between the furan and the dienophile underwent smooth cycloaddition upon thermolysis. By varying the reaction conditions, either the primary cycloadduct or the ring-opened and acetylated product could be isolated in excellent yield. The stereochemical outcome of the IMDAF cycloaddition has the side arm of the tethered alkenyl group oriented syn with respect to the oxygen bridge. Semi-empirical AM1 calculations show that the exo-cycloadduct is 11 kcal lower in energy than the corresponding endo adduct and, presumably, some of this energy difference is reflected in the transition state for the cycloaddition. The IMDAF reaction of N-allyl-[2-(3,4-dimethoxyphenethyl)]-2-furanyl-2-yl-acetamide proceeded in 90% yield upon heating in xylene. The 4+2-cycloadduct undergoes ring-opening on treatment with base and the resulting alcohol was converted into the corresponding benzyl ether. Raney nickel reduction followed by Bischler-Napieralski cyclization furnished the tetracyclic skeleton of the berberine alkaloids.Key words: intramolecular, cycloaddition, Diels-Alder, furanylamide, heterocycle.
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How this classification was reachedexpand
Full frame machine prediction
Teacher imitationNot calibrated prevalence, not ground truth. Human validation pending. The Gemma side is a direct model label for every work in the frame, read from the title-only record. The Codex side is a classifier learned from the 10,348 direct Codex labels and calibrated to design-weighted sample rates; fields without enough sample support carry no Codex call. Candidate is the union of the two sides; consensus is their intersection. These outputs are machine_predicted_unvalidated and are not human labels.
Distilled classifier scores by category (both heads)
| Category | Codex | Gemma |
|---|---|---|
| Metaresearch | 0.000 | 0.000 |
| Meta-epidemiology (narrow) | 0.000 | 0.000 |
| Meta-epidemiology (broad) | 0.000 | 0.000 |
| Bibliometrics | 0.000 | 0.000 |
| Science and technology studies | 0.000 | 0.000 |
| Scholarly communication | 0.000 | 0.000 |
| Open science | 0.000 | 0.000 |
| Research integrity | 0.000 | 0.000 |
| Insufficient payload (model declined to judge) | 0.001 | 0.001 |
Machine scores (provisional)
The two teacher heads of the student model, read on this work. A score orders the frame for review; it never asserts a category, and the validation status ships verbatim with every row.
Baseline scores from an immature model (maturity gate not passed, 7 training rounds). Scores rank; they never assert a category.
score_only:v0-immature-baseline · verbatim from the scoring run: score_only means the number may rank works, and no category label ships from itClassification
machine, unvalidatedMachine predicted; a candidate call from one source (direct Gemma or distilled Codex), not a consensus.
How this classification was reached, model by model and score by score, is at the end of the page under "How this classification was reached".