Rhodium‐Catalyzed Asymmetric Intramolecular Cyclopropanation of Substituted Allylic Cyanodiazoacetates
Why this work is in the frame
A frame that forgets how it found something cannot be audited. These are the routes that admitted this work.
Bibliographic record
Abstract
Abstract A chiral rhodium catalyst, Rh 2 [4 S ‐(4′)‐FBNAZ] 4 , was synthesized and was shown to catalyze the intramolecular cyclopropanation of substituted allylic cyanodiazoacetates. Alkenes bearing an electron‐deficient substituent including carbonyl and halogens are converted into the corresponding cyclopropanes in high yields with both chiral and achiral rhodium catalysts. The cyclopropane derivatives were generated with an enantioselectivity of up to 91% ee. For the asymmetric intramolecular cyclopropanation, cis ‐halogen‐substituted substrates afforded cyclopropanes with higher enantioselectivities than the corresponding trans diastereomers. However, only moderate enantioselectivities were observed with alkenes bearing electron‐donating groups such as alkyls. The cyclopropanation of 3‐substituted 2‐propenyl cyanodiazoacetates was strongly influenced by steric and electronic factors arising from substituents on the alkenes. For the first time, we demonstrated that the intramolecular reaction of gem ‐dihaloallylic cyanodiazoacetate afforded highly functionalized gem ‐dihalocyclopropanes. This reaction is an appealing alternative to the addition of dihalocarbenes to alkenes for the formation of gem ‐dihalocyclopropanes.
Fetched live from OpenAlex and de-inverted. Abstracts are not stored in this database: the inverted indexes are 8.6 GB of the frame’s 9.3 GB of text, and the host has 13 GB free.
Full frame distilled prediction
Teacher imitationNot calibrated prevalence, not ground truth. Human validation pending. Learned from the 10,348 direct Codex labels and 10,348 direct Gemma labels. Candidate is the union of thresholded teacher heads; consensus is their intersection. These outputs are machine_predicted_unvalidated and are not human labels or direct frontier model labels.
Codex and Gemma teacher scores by category
| Category | Codex | Gemma |
|---|---|---|
| Metaresearch | 0.000 | 0.001 |
| Meta-epidemiology (narrow) | 0.000 | 0.000 |
| Meta-epidemiology (broad) | 0.001 | 0.000 |
| Bibliometrics | 0.001 | 0.001 |
| Science and technology studies | 0.000 | 0.000 |
| Scholarly communication | 0.000 | 0.001 |
| Open science | 0.001 | 0.000 |
| Research integrity | 0.000 | 0.000 |
| Insufficient payload (model declined to judge) | 0.001 | 0.000 |
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 it