(17) reported a two-step mechanism for DMAP-catalyzed acetylation (Scheme 1); in step 1, DMAP reacts with acetic anhydride to form N-acetylated DMAP acetate (I), and in step 2, the alcohol substrate attacks I to form a transient intermediate that leads to the ester product after proton transfer and simultaneous release
DMAP attacks a carbonyl site on di-tert-butyl dicarbonate (Boc2O) resulting in tert-butyl carbonate leaving as a leaving group.
The amine attacks the carbonyl site on the boc-pyridinium species resulting in the release of DMAP (catalytic).
The base (usually TEA or DIEA) picks up the proton from the protonated amine.
This mechanism involves the formation of the acylpyridinium ion pair from the reaction of the DMAP catalyst with the acyl donor; later, the alcohol reacting with the acylated catalyst in the rate-determining second step and forming the ester product with the protonated catalyst.
A better explanation for DMAP being such an effective catalyst is that it reacts with acid chlorides, such as 12, to form high concentrations of N‑acylpyridinium salts (eq 7).
These salts are better able to transfer an acyl group to a nucleophile than is the acid chloride itself.
Activity and selectivity of DMAP derivatives in acylation reactions
19 avr. 2011 the deprotonation step in the overall reaction mechanism. [17a]. 4. The DMAP-catalyzed acetylation of tert-butanol with acetic anhydride was ... |
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3 déc. 2013 Mechanism of the sodium bicarbonate catalyzed acetylation of an alcohol using acetic anhydride. 3. Experimental Section—General Procedure. All ... |
Activity and selectivity of DMAP derivatives in acylation reactions
19 avr. 2011 the deprotonation step in the overall reaction mechanism. [17a]. 4. The DMAP-catalyzed acetylation of tert-butanol with acetic anhydride was ... |
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25 juil. 2019 2 Model esterification reaction using menthol acetic anhydride (Ac2O) |
Technical Bulletin AL-114 4-DMAP (4-Dimethylaminopyridine)
Connors and Albert recommend using acetic anhydride/-. DMAP as a reagent for the quantitiative determination of hydroxyl groups in alcohols and phenols. |
Synthesis of paracetamol by acetylation
The reaction mechanism first goes through a pre- equilibrium between DMAP and acetic anhydride forming the acetylpyridinium cation and the acetate. |
Activity and selectivity of DMAP derivatives in acylation reactions
31 mai 2011 · the deprotonation step in the overall reaction mechanism [17a] 4 The DMAP- catalyzed acetylation of tert-butanol with acetic anhydride was |
Technical Bulletin AL-114 4-DMAP (4-Dimethylaminopyridine)
ary and tertiary hydroxyl groups Connors and Albert recommend using acetic anhydride/- DMAP as a reagent for the quantitiative determination of hydroxyl |
Acetic Anhydride - Sigma-Aldrich
Acetic anhydride is an acylation reagent Acylation Pyridine may also react with acetic anhydride, however, forming N-acetyl- Mechanism (1,2) Acylation |
[PDF] Activity and selectivity of DMAP derivatives in acylation reactions
May 31, 2011 · the deprotonation step in the overall reaction mechanism [17a] 4 The DMAP catalyzed acetylation of tert butanol with acetic anhydride was |
[PDF] DMAP Pharmaceuticals and Agrochemicals - Vertellus
amines and alcohols with acetic anhydride in the presence of a base, such as pyridine, has been a well established procedure since the turn of the 20th century |
[PDF] 4‑(N,N-Dimethylamino)pyridine Hydrochloride as a Recyclable
Dec 16, 2013 · Zipse et al17 reported a two step mechanism for DMAP catalyzed acetylation ( Scheme 1); in step 1, DMAP reacts with acetic anhydride to |
[PDF] Technical Bulletin AL-114 4-DMAP (4-Dimethylaminopyridine)
Connors and Albert recommend using acetic anhydride DMAP as a reagent for the quantitiative determination of hydroxyl groups in alcohols and phenols |