40286-78-0Relevant articles and documents
Novel Preparation of Hemiaminal Derivatives with BPO and N,N-Dimethylamides and Their Synthetic Use for (Aminomethyl)indoles
Nakamura, Kohei,Togo, Hideo
, p. 4713 - 4722 (2020/08/03)
A novel preparation of hemiaminal derivatives bearing both an amide group and a benzoate group was carried out in good yields by the treatment of BPO in N,N-dimethylamides under warming condition at 80 °C or irradiation with a mercury lamp. Further treatment of the obtained hemiaminal derivatives with indoles in 1,1,1,3,3,3-hexafluoro-2-propanol generated the corresponding C–C bonded indoles bearing an amide group in good yields. The formed indoles bearing an amide group were smoothly transformed into the corresponding indoles bearing an aminomethyl group.
Kinetics and Mechanism of Hydrolysis of N-Acyloxymethyl Derivatives of Azetidin-2-one
Valente, Emilia,Gomes, Jose R. B.,Moreira, Rui,Iley, Jim
, p. 3359 - 3367 (2007/10/03)
The pH-independent, acid-catalyzed and base-catalyzed hydrolyses of N-acyloxymethylazetidin-2-ones all occur at the ester function. The pH-independent hydrolysis involves rate-limiting alkyl C-O fission and formation of an exocyclic β-lactam iminum ion. This iminium ion is then trapped by water at the exocyclic iminium carbon atom, rather than at the β-lactam carbonyl carbon atom, to form the corresponding N-hydroxymethylazetidin-2-ones. Calculations carried out at the B3LYP/6-31+G(d) level of theory also support that nucleophilic attack by water takes place at the exocyclic carbon rather than at the β-lactam carbonyl carbon of the iminium ion. The mechanism for the acid-catalyzed pathway involves a preequilibrium protonation, probably at the β-lactam nitrogen, followed by rate-limiting alkyl C-O fission with formation of an exocyclic iminum ion. The base-catalyzed hydrolysis involves rate-limiting hydroxide attack at the ester carbonyl carbon. These results imply formation of a β-lactam system containing a positively charged amide nitrogen atom that hydrolyzes via a pathway that preserves the β-lactam structure in the product and provide further evidence that cleavage of the β-lactam C-N bond is not as facile as is commonly imagined.
