Chemoselective aromatic azido reduction with concomitant aliphatic azide employing Al/Gd triflates/NaI and ESI-MS mechanistic studies.
Aluminium and gadolinium triflates catalyze the chemoselective reduction of aromatic azides to the corresponding amines in combination with sodium iodide. This mild chemoselective method has been applied to the synthesis of various aryl amines, C2-azido-substituted pyrrolo[2,1-c][1,4]benzodiazepines, and fused[2,1-b]quinazolinones by an intramolecular azido reduction tandem cyclization reaction. Interestingly, this methodology selectively reduces aryl azides with enhanced yields and proceeds in shorter reaction times than previous strategies. The mechanistic aspects have been investigated and the intermediates associated with this selective transformation have been intercepted and characterized by online monitoring of the reaction by ESI-MS.
Kamal
Ahmed
A
Chemical Biology Laboratory, Indian Institute of Chemical Technology, Hyderabad 500 007, India.
Markandeya
Nagula
N
Shankaraiah
Nagula
N
Reddy
C Ratna
CR
Prabhakar
S
S
Reddy
C Sanjeeva
CS
Eberlin
Marcos N
MN
Silva Santos
Leonardo
L
D000535:Aluminum / Q000737:chemistry*; D000588:Amines / Q000737:chemistry*; D001386:Azides / Q000138:chemical synthesis* / Q000737:chemistry*; D001569:Benzodiazepines / Q000138:chemical synthesis* / Q000737:chemistry; D002104:Cadmium / Q000737:chemistry*; D002384:Catalysis; D003500:Cyclization; D006571:Heterocyclic Compounds / Q000138:chemical synthesis* / Q000737:chemistry*; D015394:Molecular Structure; D010084:Oxidation-Reduction; D052999:Quinazolinones / Q000138:chemical synthesis* / Q000737:chemistry; D012974:Sodium Iodide / Q000737:chemistry*; D021241:Spectrometry, Mass, Electrospray Ionization; D013237:Stereoisomerism
D000588:Amines; D001386:Azides; D006571:Heterocyclic Compounds; D052999:Quinazolinones; D002104:Cadmium; D001569:Benzodiazepines; D000535:Aluminum; D012974:Sodium Iodide