Diamine Ligands for Room-Temperature Ullmann-Type Cross-Coupling

Three diamine ligands from TCI, N-([1,1'-biphenyl]-2-yl)-N'-(2-phenylnaphthalen-1-yl)-benzene-1,2-diamine (B6606), N1-(3',5'-di-tert-butyl-[1,1'-biphenyl]-2-yl)-N2-(2-(3,5-di-tert-butylphenyl)naphthalen1-yl)benzene-1,2-diamine (D6240), and N,N'-Bis(2-phenylnaphthalen-1-yl)benzene-1,2-diamine (B6801), enable copper-catalysed Ullmann-type cross-coupling of aryl bromides at room temperature with CuI as the copper catalyst. These diamine ligand systems avoid expensive metals such as palladium and proceed under milder conditions than conventional Ullmann couplings, which typically require high temperatures. B6606 is effective for C(sp2)-N coupling of aryl bromides with primary and secondary amines (both cyclic and acyclic) with relatively small steric hindrance.²) D6240 is particularly effective for bulky substrates, such as ortho-substituted aryl bromides with morpholine, and its tert-butyl groups prevent self-degradation of the ligand.²) B6801 enables C(sp2)-O coupling of aryl bromides with alcohols, C(sp2)-N coupling with the weak base NaOTMS, and coupling with base-sensitive five-membered heteroarenes. It also allows switching N/O selectivity depending on the base.³) ⁴)

Related products

• TCI B6606 2897656-97-0 N1-([1,1'-Biphenyl]-2-yl)-N2-(2-phenylnaphthalen-1-yl)benzene-1,2-diamine
• TCI D6240 N1-[3',5'-Di-tert-butyl-[1,1'-biphenyl]-2-yl]-N2-[2-(3,5-di-tert-butylphenyl)naphthalen-1-yl]benzene-1,2-diamine
• TCI B6801 3035177-77-3 N,N'-Bis(2-phenyl-1-naphthyl)-1,2-benzenediamine
• TCI C2163 7681-65-4 Copper(I) Iodide

References

1. Q. Yang, Y. Zhao, D. Ma, Org. Proc. Res. Dev. 2022, 26, 1690. doi:https://doi.org/10.1021/acs.oprd.2c00050
2. S. Kim, M. J. Strauss, A. Cabré, S. L. Buchwald, J. Am. Chem. Soc. 2023, 142, 6966. doi:https://doi.org/10.1021/jacs.3c00500
3. M. J. Strauss, S. L. Buchwald, et al., Angew. Chem. Int. Ed. 2024, 63, e202400333. doi:https://doi.org/10.1002/anie.202400333
4. M. J. Strauss, S. L. Buchwald, et al., J. Am. Chem. Soc. 2024, 146, 18616. doi:https://doi.org/10.1021/jacs.4c05246

Download TCI brochure Diamine Ligands for Ullmann-Type Cross-Coupling at Room Temperature (PDF)

Ask AMI via WhatsApp

Source

• TCI Product Highlights: www.tcichemicals.com/ID/en/product/tci-topics/ProductHighlights_20250728
• TCI product page B6606: tcichemicals.com/ID/en/p/B6606
• TCI product page B6801: tcichemicals.com/ID/en/p/B6801
• TCI product page D6240: tcichemicals.com/ID/en/p/D6240

For research and laboratory use only, not for human consumption.