Reactions of Tertiary Aliphatic Cations with Silylated Alkynes: Substitution, Cyclization and Unexpected C−H Activation Products
Bibliographic record
Abstract
Capozzi's groundbreaking work in 1982 introduced a fascinating reaction involving highly reactive tertiary aliphatic cations and silylated alkynes. This reaction provided an innovative solution to the challenge of coupling a fully substituted tertiary aliphatic fragment with an alkyne moiety. Building upon Capozzi's pioneering efforts, we started an extensive exploration of reaction conditions to expand the initial scope of this reaction. Through meticulous control of the reaction parameters, we uncovered conditions capable of accommodating various functional groups, thereby enhancing the reaction's applicability. Intriguingly, our study revealed remarkably high diastereoselectivities for substrates with substitution in the α-position. Additionally, we made an unexpected discovery: an intriguing C-H activation of a cyclooctane ring furnishing a cyclooctane-fused cyclobutene. These findings not only extend the utility of Capozzi's original concept but also underscore the potential of highly reactive cations in modern organic C-H activation reactions.
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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 | 0.001 |
| 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) | 0.000 | 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".