Oxidative generation of reactive iminium-intermediates: A powerful strategy for C-H bond functionalization
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
This thesis is an investigation on the generation and reactivity of carbocations adjacent to a trisubstituted nitrogen atom (iminium).In the first part of this thesis, a copper-catalyzed oxidative alkylation of sp 3 C-H bond adjacent to a nitrogen atom is described.This environmentally respectful process used molecular oxygen as oxidant and water as solvent.In the second part of the thesis, an aerobic sp 3 C-H bond phosphonation reaction is presented.This process catalyzed by copper(I) bromide using dialkylphosphites as nucleophiles offered direct C-P bond formation via direct oxidative coupling of C-H and P-H bonds.In the third part of the thesis, a copper-catalyzed sp 3 C-H bond arylation with boronic acids in absence of directing group is described.The oxidative arylation reaction provided easy access to biologically active tetrahydroisoquinoline derivatives and can either use peroxide or molecular oxygen as oxidant.In the last part of the thesis, the aerobic and electrochemical Cross-Dehydrogenative-Coupling in ionic liquids is presented.Ionic liquids have demonstrated high efficiency when applied as solvent and electrolyte solvent for the oxidative nitro-Mannich carbon-carbon bond formation.
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 | 0.001 | 0.001 |
| Meta-epidemiology (narrow) | 0.001 | 0.001 |
| Meta-epidemiology (broad) | 0.001 | 0.000 |
| Bibliometrics | 0.001 | 0.001 |
| Science and technology studies | 0.001 | 0.000 |
| Scholarly communication | 0.000 | 0.001 |
| Open science | 0.001 | 0.000 |
| Research integrity | 0.001 | 0.001 |
| 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 it