Buchwald–Hartwig amination: 4-Bromo-2-fluorobenzaldehyde → tert-butyl N-(3-fluoro-4-formylphenyl)carbamate
97% yield, run at 100 °C, as recorded by experimental reaction archive. The written procedure is below.
The atoms, from reactants to products
What was in the flask
| Role | Species | Formula | Yield |
|---|---|---|---|
| Reactant | 4-Bromo-2-fluorobenzaldehyde | C₇H₄BrFO | |
| Reactant | tert-Butyl carbamate | C₅H₁₁NO₂ | |
| Reagent | Cesium carbonate | CCs₂O₃ | |
| Catalyst | Binap, (A+-)- | C₄₄H₃₂P₂ | |
| Catalyst | (1E,4E)-1,5-diphenylpenta-1,4-dien-3-one; palladium | C₃₄H₂₈O₂Pd | |
| Solvent | Toluene | C₇H₈ | |
| Product | tert-butyl N-(3-fluoro-4-formylphenyl)carbamate | C₁₂H₁₄FNO₃ | 97.47% |
Conditions
- Temperature
- 100 °C
Yield
- 97% of tert-butyl N-(3-fluoro-4-formylphenyl)carbamate.
Other recorded runs with the same starting material
No other run in the library makes this product. These runs of the same class start from one of the same reactants, which is the nearest company this record has.
- tert-butyl N-(5-chloropyridazin-3-yl)carbamate100%
- tert-butyl N-(3-fluoro-5-methyl-2-pyridinyl)carbamate26%
- 2-(Tert-butoxycarbonylamino)-6-chloroisonicotinic acid0%
- N-[5-amino-4-methoxy-2-(4-methyl-1-piperazinyl)phenyl]carbamic acid 1,1-dimethylethyl ester0%
- (4-Hydroxymethyl-6-methyl-pyridine-2-yl)-carbamic acid tert-butyl ester0%
- tert-Butyl (5-fluoro-6-methylpyridin-2-yl)carbamate0%
- 3-(Boc-amino)pyridinenot recorded
- tert-butyl N-(3-fluoro-5-methyl-2-pyridinyl)carbamate26%
- 3-(Boc-amino)pyridinenot recorded
- 3-(Boc-amino)pyridinenot recorded
- 3-(Boc-amino)pyridinenot recorded
- 3-(Boc-amino)pyridinenot recorded
Procedure
Copied from the source record, unedited
A solution of 4-bromo-2-fluorobenzaldehyde (3.09 g, 15.22 mmol) dissolved in toluene (40 mL) was treated with tert-butyl carbamate (2.140 g, 18.27 mmol), rac-2,2'-Bis(diphenylphosphino)-1,1'-binaphthyl (0.758 g, 1.22 mmol), Bis(dibenzylideneacetone)palladium (0.350 g, 0.61 mmol) and cesium carbonate (7.04 g, 21.62 mmol) under nitrogen. The mixture was degassed under vacuum several times before heating at 100 °C for 30 hours. The reaction mixture was diluted with water (250 mL), and extracted with ethyl acetate (250 mL X 2). The organic was dried over magnesium sulfate, filtered and evaporated to afford crude product. The crude product was purified by flash silica chromatography, elution 10% ethyl acetate in isohexane. Pure fractions were evaporated to dryness to afford tert-butyl 3-fluoro-
The source
This record comes from experimental reaction archive (ord-122adeafa04f44969e42186d0dc6c6bd). Open the source and check it against what is on this page.
experimental reaction archive record ord-122adeafa04f44969e42186d0dc6c6bd 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.