Buchwald–Hartwig amination: 2-Bromoanisole → Tert-butyl 4-(2-methoxyphenyl)piperazine-1-carboxylate
62% yield, run at 100 °C, as recorded by experimental reaction archive. The written procedure is below. One of 2 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 | 2-Bromoanisole | C₇H₇BrO | |
| Reactant | tert-Butyl piperazine-1-carboxylate | C₉H₁₈N₂O₂ | |
| Reagent | sodium 2-methylpropan-2-olate | C₄H₉NaO | |
| Catalyst | Binap, (A+-)- | C₄₄H₃₂P₂ | |
| Catalyst | Bis(dibenzylideneacetone)palladium | C₅₁H₄₂O₃Pd₂ | |
| Solvent | Toluene | C₇H₈ | |
| Product | Tert-butyl 4-(2-methoxyphenyl)piperazine-1-carboxylate | C₁₆H₂₄N₂O₃ | 62.37% |
Conditions
- Temperature
- 100 °C
Yield
- 62% of Tert-butyl 4-(2-methoxyphenyl)piperazine-1-carboxylate.
Every recorded run making this product
2 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.
| Reactants | Catalyst | Reagents | Solvent | Temp. | Time | Yield |
|---|---|---|---|---|---|---|
| 2-Bromoanisole; tert-Butyl piperazine-1-carboxylate | Binap, (A+-)-; Bis(dibenzylideneacetone)palladium | sodium 2-methylpropan-2-olate | Toluene | 100 °C | — | 62% (this run) |
| 2-Chloroanisole; tert-Butyl piperazine-1-carboxylate | 2-Dicyclohexylphosphino-2',6'-diisopropoxybiphenyl; Palladium (II) acetate | sodium 2-methylpropan-2-olate | Toluene | 100 °C | — | 11% |
Procedure
Copied from the source record, unedited
TRIS(DIBENZYLIDENEACETONE)DIPALLADIUM(0) (0.059 g, 0.06 mmol) and 2,2'-bis(diphenylphosphino)-1,1'-binaphthyl (0.080 g, 0.13 mmol) were mixed in toluene (10 mL) and degessed at 90 °C for 10 mins. The mixture was then cooled and 1-bromo-2-methoxybenzene (0.400 mL, 3.21 mmol), sodium 2-methylpropan-2-olate (0.493 g, 5.13 mmol) and tert-butyl piperazine-1-carboxylate (0.597 g, 3.21 mmol) were added. The resulting mixture was stirred at 100 °C for 16 hours under nitrogen. The reaction mixture was filtered through celite and the filtrate concentrated. The crude product was purified by flash silica chromatography, elution gradient 20 to 100% EtOAc in heptane. Pure fractions were evaporated to dryness to afford tert-butyl 4-(2-methoxyphenyl)piperazine-1-carboxylate (0.585 g, 62.4 %) as a yellow o
The source
This record comes from experimental reaction archive (ord-636da506499347d7aba99b6e3204f5ba). Open the source and check it against what is on this page.
experimental reaction archive record ord-636da506499347d7aba99b6e3204f5ba 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.
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