Buchwald–Hartwig amination: 4-chloro-N-phenylpyridin-2-amine → 4-N-benzyl-2-N-phenylpyridine-2,4-diamine
6% yield, run at 100 °C, as recorded by experimental reaction archive. The written procedure is below. One of 3 recorded runs making this product; all of them are compared below.
The atoms, from reactants to products
What was in the flask
| Role | Species | Formula | Yield |
|---|---|---|---|
| Reactant | 4-chloro-N-phenylpyridin-2-amine | C₁₁H₉ClN₂ | |
| Reactant | Benzylamine | C₇H₉N | |
| Reagent | sodium 2-methylpropan-2-olate | C₄H₉NaO | |
| Catalyst | Brettphos | C₃₅H₅₃O₂P | |
| Catalyst | Palladium (II) acetate | C₄H₈O₄Pd | |
| Solvent | Dimethylacetamide | C₄H₉NO | |
| Product | 4-N-benzyl-2-N-phenylpyridine-2,4-diamine | C₁₈H₁₇N₃ | 6.32% |
Conditions
- Temperature
- 100 °C
Yield
- 6% of 4-N-benzyl-2-N-phenylpyridine-2,4-diamine.
Every recorded run making this product
3 runs of this class made the same product and differed in what else was in the flask. They are listed from the highest yield down, with this page's run marked.
| Catalyst | Reagents | Solvent | Temp. | Time | Yield |
|---|---|---|---|---|---|
| (R)-(-)-1-[(S)-2-(Dicyclohexylphosphino)ferrocenyl]ethyldi-t-butylphosphine;Ferrocene, 1-[(1R)-1-[bis(1,1-dimethylethyl)phosphino]ethyl]-2-(dicyclohexylphosphino)-, (2R)-; Palladium (II) acetate | sodium 2-methylpropan-2-olate | Dimethylacetamide | 100 °C | — | 57% |
| 2-Dicyclohexylphosphino-2',6'-diisopropoxybiphenyl; Palladium (II) acetate | sodium 2-methylpropan-2-olate | Dimethylacetamide | 100 °C | — | 13% |
| Brettphos; Palladium (II) acetate | sodium 2-methylpropan-2-olate | Dimethylacetamide | 100 °C | — | 6% (this run) |
Procedure
Copied from the source record, unedited
Phenylmethanamine (57.6 mg, 0.54 mmol), 4-chloro-N-phenylpyridin-2-amine (100 mg, 0.49 mmol) and sodium 2-methylpropan-2-olate (94 mg, 0.98 mmol) were suspended in DMA (2 mL) and sealed into a microwave tube. Nitrogen was bubbled through the reaction mixture for 5 minutes. Dicyclohexyl(2',4',6'-triisopropyl-3,6-dimethoxy-[1,1'-biphenyl]-2-yl)phosphine (31.5 mg, 0.06 mmol) and diacetoxypalladium (8.78 mg, 0.04 mmol) were added to the reaction mixture and nitrogen was bubbled through the reaction mixture for a further 5 minutes. The reaction was heated thermally to 100 °C for 30 mins under nitrogen and cooled to RT. The reaction mixture was neutralised with HCl and purified by ion exchange chromatography, using a 20 g SCX column. The crude product was purified by preparative HPLC (Waters Sun
The source
This record comes from experimental reaction archive (ord-34a984f4da874bc6bcf03a1eda073eec). Open the source and check it against what is on this page.
experimental reaction archive record ord-34a984f4da874bc6bcf03a1eda073eec from dataset "750 AstraZeneca ELN dataset" (url: https://chemrxiv.org/engage/chemrxiv/article-details/60c9e3f37792a23bfdb2d471). No atom mapping is provided by the source.
How to read this record
This is one experiment, not a rule. It says that on one occasion these species were combined under these conditions and this came out. It does not say the reaction will give the same result on your substrate, and nothing on the page has been generalised into a claim that it would.
The pathway is a separate question, kept on separate pages. A mechanism here is the canonical arrow pushing for a class, run on real structures and labelled rule-derived. It is not evidence, and this record is not a mechanism.
Where to next
More Buchwald–Hartwig amination records
Other runs of this class, one page per distinct transformation.
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