1. Speaker: Chien-An Chen Teacher: Guey-Sheng Liou
Direct Arylation
Speaker: Chien-An Chen
Teacher: Guey-Sheng Liou

2. Important bi(hetero)aryls

3. Direct Arylation V.S. Traditional Cross-Coupling
Define of direct arylation:
Through cleavage of C-H bond
Advantage of direct arylation:
Without metallic halides by-product
→good for enviorment
Reduce the synthetic operations
→economical

4. Category of Direct Arylation

5. Direct Arylation with Organometallic Reagents (Rh-cat.)

6. Direct Arylation with Organometallic Reagents (Pd-cat.)

7. Direct Arylation with Organometallic Reagents (Ru-cat.)

8. Dehydrogenative Arylation

9. Direct Arylation with (Pseudo)Halides (Pd-cat.)

10. Direct Arylation on LBG polymer
Ullrich Scherf et al. , ACS Macro Lett. 2012, 1, 465−468

11. Direct Arylation on LBG polymer
Takaki Kanbara et al. , ACS Macro Lett. 2012, 1, 67−70

12. Direct Arylation on LBG polymer
Disadvantage:
The critical factor of direct arylation polymerization is regioselectivity. Example:
Solution method: Use protecting group, methyl, to protect 3-position of thiophene. Example:
The two hydrogen atoms are also reactive
Cross-linked polymer

13. Conclusion
Until very recently, the majority of catalytic direct arylations have been accomplished with palladium, rhodium, or ruthenium catalysts. However, less-expensive copper, iron, and nickel compounds have been shown.
The use of atom-economical terminal oxidants and achieving regioselectivity in intermolecular arylations remain significant challenges.