Divergent Synthesis of 1,2,3,4‐Tetrasubstituted Cyclobutenes from a Common Scaffold: Enantioselective Desymmetrization by Dual‐Catalyzed Photoredox Cross‐Coupling
Bibliographic record
Abstract
Abstract Four‐membered carbocycles are important structural motifs found in several natural products and drugs. Amongst those, cyclobutenes are attractive intermediates because the residual olefin can be manipulated selectively into various saturated and unsaturated analogs. Few methods exist to access chiral tri‐ and tetra‐C‐substituted cyclobutenes and they are generally limited in terms of diversification. Herein, a divergent synthetic strategy was developed where a single optically enriched scaffold is diversified into a variety of derivatives with different substitution patterns. To this end, the enantioselective desymmetrization of prochiral 1,2‐dibromocyclobutene imides was enabled by a dual Ir/Ni‐catalyzed photoredox C(sp2)−C(sp3) cross‐coupling with an alkyltrifluoroborate salt to install a convertible carbon fragment in good yields and >90 % enantiomeric excess. Exceptional mono‐coupling selectivity is observed and the resulting chiral bromocyclobutene serves as a common scaffold that can be transformed in a divergent manner into several valuable 1,2,3,4‐tetra‐C‐substituted cyclobutane products while maintaining optical purity.
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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) | 0.001 | 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 | 0.001 |
| 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".