New Borylation Strategy for the Construction of Borylated Heterocycles and Bodipy Derivatives
Bibliographic record
Abstract
This thesis mainly concerns: (1) developing new borylation strategies for heterocycles through addition of a B-E σ bond (E = H, N) across internal alkynes; (2) synthesizing BODIPY derivatives with interesting properties via “pre-functionalization” strategy; (3) preparing boron-based stimuli-responsive compounds for fluoride sensing. The hydroboration of alkynes is known to proceed in a cis-fashion. Catalytic trans-hydroboration has been established in the past decade while catalyst-free trans-hydroboration was unknown. In the study of hydroboration reactions, an unexpected pyridine-directed trans-hydroboration of internal alkynes was disclosed and presented. This transformation could serve as a facile method to construct novel luminescent N,C-chelate organoboron compounds. In the study of the amine directed hydroboration reaction, a facile dehydrogenative coupling between alkynyl aryl amines and 9-BBN was discovered. Based on the dehydrogenated products, a catalytic trans-aminoboration of internal alkynes was designed to give borylated indole derivatives. The reaction scope to different boranes and anilines was surveyed to generate a variety of borylated indoles. The dehydrogenative coupling of arylamines with 9-BBN described above represents a convenient method to construct a B-N covalent bond. By switching 9-BBN to monosubstituted boranes, a family of novel azaborabenzofulvenes was obtained by exploiting sequential dehydrogenative hydroboration of alkynyl arylamines. Both the reaction scope and the properties of the products were studied. Boron-dipyrromethene (BODIPY) and derivatives are excellent luminophores with bright emission in dilute solutions. However, they are rarely emissive in the solid state. In chapter 5, several spiro-BODIPYs with the “pre-functionalization” strategy were prepared. The spiro-structure successfully precludes the formation of π-stacking and leads to efficient solid state emissions. More interestingly, the spiro-BODIPYs formed J-aggregates in methanol-water mixed solvents. With the same strategy, a ferrocene functionalized BODIPY featuring direct Fc-B bond was prepared. Detailed studies on the novel compound and its analogues indicate the importance of ferrocenyl substituents and the bridge on their excited-state properties of BODIPY molecules. Trivalent organoboranes have been explored as fluoride sensors by monitoring fluorescence change, which is inconvenient in practical applications. In chapter 7, a family of boron functionalized poly-ferrocene compounds were prepared and some of these molecules can be used for colorimetric fluoride sensing.
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 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) | 0.000 | 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 | 0.000 | 0.000 |
| Research integrity | 0.000 | 0.001 |
| Insufficient payload (model declined to judge) | 0.002 | 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".