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Buchwald–Hartwig amination, record ord-879a784e2da64b7f993840feec5d14ac

One recorded run of this reaction. Below is what the source recorded, and nothing added to it.

verified record91% yield recordedNot balanced as writtenFrom experimental reaction archive

Reactants and products as the record gives them. Reagents, catalysts and solvents are listed below rather than drawn.

Open this record in the Reaction LabThe atom map, the animation and the records that run the same transformation.

What was in the flask

RoleSpeciesFormulaYield
ReactantMethyl 4-Bromo-2-chlorobenzoateC₈H₆BrClO₂
Reactanttert-Butyl piperazine-1-carboxylateC₉H₁₈N₂O₂
ReagentCesium carbonateCCs₂O₃
CatalystBinap, (A+-)-C₄₄H₃₂P₂
CatalystPalladium (II) acetateC₄H₈O₄Pd
SolventTolueneC₇H₈
ProductMethyl 4-(4-Boc-1-piperazinyl)-2-chlorobenzoateC₁₇H₂₃ClN₂O₄90.88%

The equation does not balance as written. That is usual for an experimental record: the source listed what it put in and what it measured, not a stoichiometric equation.

Conditions

Temperature
80 °C

Only the dimensions the source stated are listed. Anything absent here was not recorded, and it is not inferred from what the class usually needs.

Yield

  • 91% of Methyl 4-(4-Boc-1-piperazinyl)-2-chlorobenzoate.

Procedure

Copied from the source record, unedited

To a solution of palladium acetate (18.00 mg, 0.08 mmol) in dry toluene (16 mL) under nitrogen was added BINAP (100 mg, 0.16 mmol). The reaction was heated to 80 °C and stirred for 10 min. To the reaction was then added tert- butyl piperazine-1-carboxylate (299 mg, 1.60 mmol), cesium carbonate (261 mg, 0.80 mmol), potassium carbonate (222 mg, 1.60 mmol), 18-crown-6 (42.4 mg, 0.16 mmol) and methyl 4-bromo-2-chlorobenzoate (400 mg, 1.60 mmol). The reaction was stirred at 80°C overnight, filtered through celite and washed with small amounts of DCM. The filtrate was concentrated under reduced pressure and purified by flash chromatography on silica gel, eluting with mixtures of EtOAc and heptane, to afford tert-butyl 4-(3-chloro-4-(methoxycarbonyl)phenyl)piperazine-1-carboxylate (517 mg, 91 %)

The source

This record comes from experimental reaction archive (ord-879a784e2da64b7f993840feec5d14ac). Open the source and check it against what is on this page.

  • experimental reaction archive record ord-879a784e2da64b7f993840feec5d14ac from dataset "750 AstraZeneca ELN dataset" (url: https://chemrxiv.org/engage/chemrxiv/article-details/60c9e3f37792a23bfdb2d471). No atom mapping is provided by the source.

    experimental record · quality medium · source

experimental reaction record.

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.