Aziridine synthesis - Organic chemistry

Kinetics and Mechanism of Aziridine Synthesis from Ketoxime with Lithium Aluminum Hydride

A mechanism to explain this novel ..

N2 - The synthesis, spectral, and reactivity properties of 6-methoxy- and 7-methoxyindano[1,2-b]aziridines (8 and 9, respectively) are detailed. Hydrolysis of each aziridine produced the corresponding trans- and cis-2-amino-1-indanols in approximately 1:2 ratio, respectively. The 7-methoxy adduct 9 underwent hydrolysis approximately 250 times faster than the isomeric 6-methoxyaziridine 8 at pH 8.88. Both the product profiles and the kinetic rate data for the hydrolysis of 8 and 9 are consistent with a mechanism in which protonation of the aziridine precedes the rate-determining ring-opening step to generate the corresponding benzylic cation. The products generated in these reactions paralleled those reported for the hydrolysis of the antineoplastic agent mitomycin C under reductive conditions. The implications of these findings in relation to the mode of action of mitomycin C are discussed.

Aziridine synthesis by ring closure reaction

AB - The synthesis, spectral, and reactivity properties of 6-methoxy- and 7-methoxyindano[1,2-b]aziridines (8 and 9, respectively) are detailed. Hydrolysis of each aziridine produced the corresponding trans- and cis-2-amino-1-indanols in approximately 1:2 ratio, respectively. The 7-methoxy adduct 9 underwent hydrolysis approximately 250 times faster than the isomeric 6-methoxyaziridine 8 at pH 8.88. Both the product profiles and the kinetic rate data for the hydrolysis of 8 and 9 are consistent with a mechanism in which protonation of the aziridine precedes the rate-determining ring-opening step to generate the corresponding benzylic cation. The products generated in these reactions paralleled those reported for the hydrolysis of the antineoplastic agent mitomycin C under reductive conditions. The implications of these findings in relation to the mode of action of mitomycin C are discussed.

The synthesis, spectral, and reactivity properties of 6-methoxy- and 7-methoxyindano[1,2-b]aziridines (8 and 9, respectively) are detailed. Hydrolysis of each aziridine produced the corresponding trans- and cis-2-amino-1-indanols in approximately 1:2 ratio, respectively. The 7-methoxy adduct 9 underwent hydrolysis approximately 250 times faster than the isomeric 6-methoxyaziridine 8 at pH 8.88. Both the product profiles and the kinetic rate data for the hydrolysis of 8 and 9 are consistent with a mechanism in which protonation of the aziridine precedes the rate-determining ring-opening step to generate the corresponding benzylic cation. The products generated in these reactions paralleled those reported for the hydrolysis of the antineoplastic agent mitomycin C under reductive conditions. The implications of these findings in relation to the mode of action of mitomycin C are discussed.