Buchwald–Hartwig amination: 3-Bromopyridine → Tert-butyl 4-(pyridin-3-YL)piperazine-1-carboxylate
29% yield, run at 85 °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 | 3-Bromopyridine | C₅H₄BrN | |
| 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-(pyridin-3-YL)piperazine-1-carboxylate | C₁₄H₂₁N₃O₂ | 29.23% |
Conditions
- Temperature
- 85 °C
Yield
- 29% of Tert-butyl 4-(pyridin-3-YL)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.
| Catalyst | Reagents | Solvent | Temp. | Time | Yield |
|---|---|---|---|---|---|
| 2-Dicyclohexylphosphino-2',6'-diisopropoxybiphenyl; Palladium (II) acetate | sodium 2-methylpropan-2-olate | 1,4-Dioxane | 100 °C | — | 38% |
| Binap, (A+-)-; Bis(dibenzylideneacetone)palladium | sodium 2-methylpropan-2-olate | Toluene | 85 °C | — | 29% (this run) |
Procedure
Copied from the source record, unedited
TRIS(DIBENZYLIDENEACETONE)DIPALLADIUM(0) (0.059 g, 0.06 mmol) and rac-2,2'-bis(diphenylphosphino)-1,1'-binaphthyl (0.080 g, 0.13 mmol) were mixed together and evacuated and purged with nitrogen 3 times. toluene (31.6 ml) was added and the resulting mixture heated to 90°C for 10 minutes then cooled to room temperature. sodium tert-butoxide (0.465 g, 4.84 mmol), 3-bromopyridine (0.310 ml, 3.22 mmol) and tert-butyl piperazine-1-carboxylate (0.6 g, 3.22 mmol) were added and the resulting mixture was heated at 85 °C for 64 hours. The reaction mixture was cooled to RT and filtered through celite and concentrated to give an orange solid. The crude product was purified by flash silica chromatography, elution gradient 30 to 50% EtOAc in heptane. Pure fractions were evaporated to dryness to afford t
The source
This record comes from experimental reaction archive (ord-7977e1a392644e76ab21a7fab838843f). Open the source and check it against what is on this page.
experimental reaction archive record ord-7977e1a392644e76ab21a7fab838843f 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.
Open in the Reaction Lab
The atom map, the bonds that break and form, and records running the same transformation.
Percent yield calculator
Work out a yield from what you isolated against what the equation allows.
Molecules A–Z
Every named molecule, with its identifiers and sources.