Unique Diastereoselectivity Trends in Aminyl Radical Cyclizations onto Silyl Enol Ethers
Bibliographic record
Abstract
The cyclization of nitrogen-centered radicals onto silyl enol ethers is an efficient method for the synthesis of polyhydroxylated alkaloids as the 2-hydroxymethylpyrrolidine core can be readily accessed from a linear precursor. During our studies on the synthesis of polyhydroxylated alkaloid CYB-3, we found that the diastereoselectivity of the cyclization was dependent on a complex combination of sterics and olefin geometry. A more thorough understanding of the factors that lead to high diastereoselectivites would greatly expand the utility of this methodology in complex natural product synthesis. We have found that cyclization diastereoselectivities of substrates with alkyl or aryl substitution were excellent regardless of olefin geometry or substitution pattern. When electronegative substituents were introduced adjacent to the silyl enol ether, only Z-silyl enol ethers provide high diastereoselectivites. Temperature, steric size of the silyl group, and sterics and electronics of the metal hydride affected the selectivity to a lesser extent.
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.
How this classification was reachedexpand
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) | 0.000 | 0.000 |
| Bibliometrics | 0.000 | 0.000 |
| Science and technology studies | 0.000 | 0.000 |
| Scholarly communication | 0.000 | 0.000 |
| Open science | 0.001 | 0.000 |
| Research integrity | 0.000 | 0.001 |
| Insufficient payload (model declined to judge) | 0.004 | 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 itClassification
machine, unvalidatedMachine predicted; a candidate call from one teacher head, 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".