Direct (Hetero)Arylation: A New Tool for Polymer Chemists
Bibliographic record
Abstract
The coupling of aryl halides with catalytically activated aryl C-H bonds provides a desirable and atom-economical alternative to standard cross-coupling reactions for the construction of new C-C bonds. The reaction, termed direct (hetero)arylation, is believed to follow a base-assisted, concerted metalation-deprotonation (CMD) pathway. During this process, carboxylate or carbonate anions coordinate to the metal center, typically palladium, in situ and assist in the deprotonation transition state. Researchers have employed this methodology with numerous arenes and heteroarenes, including substituted benzenes, perfluorinated benzenes, and thiophenes. Thiophene substrates have demonstrated high reactivity toward C-H bond activation when appropriately substituted with electron-rich and/or electron-deficient groups. Because of the pervasive use of thiophenes in materials for organic electronics, researchers have used this chemistry to modularly prepare conjugated small molecules and, more recently, conjugated polymers. Although optimization of reaction conditions such as solvent system, phosphine ligand, carboxylate additives, temperature, and time is necessary for efficient C-H bond reactivity of each monomer, direct (hetero)arylation polymerization (DHAP) can afford high yielding polymeric materials with elevated molecular weights. The properties of these materials often rival those of polymers prepared by traditional methods. Moreover, DHAP provides a facile means for the synthesis of polymers that were previously inaccessible or difficult to prepare due to the instability of organometallic monomers. The major downfall of direct (hetero)arylation, however, is the lack of C-H bond selectivity, particularly for thiophene substrates, which can result in cross-linked material during polymerization reactions. Further fine-tuning of reaction conditions such as temperature and reaction time may suppress these unwanted side reactions. Alternatively, new monomers can be designed where other reactive bonds are blocked, either sterically or by substitution with unreactive alkyl or halogen groups. In this Account, we illustrate these methods and present examples of DHAP reactions that involve the preparation of common homopolymers used in organic electronics (P3HT, PEDOT, PProDOT), copolymers formed by activation of electron-rich (bithiophene, fused bithiophenes) and electron-deficient monomers (TPD, 1,2,4,5-tetrafluorobenzene, 2,2'-bithiazole). Our group is optimizing these reactions and developing ways to make DHAP a common atom-economical synthetic tool for polymer chemists.
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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 | 0.002 | 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 | 0.004 |
| Scholarly communication | 0.002 | 0.008 |
| Open science | 0.001 | 0.003 |
| Research integrity | 0.002 | 0.007 |
| Insufficient payload (model declined to judge) | 0.007 | 0.005 |
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".