Directing Influence of Proximal Boron Functionalities on the S-Alkylation of Sulfenic Acid Anions: An Experimental and Computational Study
Bibliographic record
Abstract
The S-functionalization chemistry of sulfenic acid anions, also known as sulfenate anions, represents an emerging method for the preparation of sulfoxides. Nearby functional groups can often influence the S-functionalization chemistry of sulfenate anions through nonbonding interactions. Recently, several reports have illustrated the combination of the Lewis acidity of trivalent boron and Lewis basicity of sulfinyl groups to perform valuable chemistry, but limited experimental investigations into the Lewis acid/Lewis base complex between sulfenate anions and trivalent boron functionalities have been conducted. In this paper, the interaction between sulfenate anions and trivalent boron functionalities is investigated using sulfenate S-functionalization competition reactions between ortho -borylated and nonborylated benzyl electrophiles. In 22 competition experiments with varied sulfenate anions and electrophilic boron species, sulfenate anion S-functionalization reactions were up to 100% selective for an ortho -borylated benzyl bromide electrophile. DFT computational modeling experiments, 11 B NMR tracking experiments, Hammett correlation analysis, and control experiments were conducted to investigate the origin of the observed selectivities, and these provided evidence that the formation of a Lewis acid/Lewis base complex between the sulfenate oxygen and the trivalent boron prior to intramolecular sulfenate S-functionalization is a major factor in establishing the selectivity.
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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 | 0.001 | 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 | 0.000 |
| 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".