Mechanistic investigation of enolate/stabilized vinylogous carbanion-mediated organocatalytic azide (3+2) cycloaddition reactions for the synthesis of 1,2,3-triazoles

Author(s)

Chiavegatti Neto, Attilio ; Soares, Kelly Cintra ; Santos, Maiara da Silva ; Aimola, Tulio Jardini ; Ferreira, Antonio Gilberto ; Jardim, Guilherme A. M. ; Tormena, Claudio Francisco ; Paixao, Marcio Weber ; Barbosa Ferreira, Marco Antonio

• Document type: Journal article
• Source: ORGANIC & BIOMOLECULAR CHEMISTRY; v. N/A, p. 8-pg., 2022-03-30.

Abstract

Herein, we report a fully detailed mechanistic study involving an organocatalyzed 1,3-dipolar cycloaddition via enolate or stabilized vinylogous carbanion intermediates and azide for the synthesis of 1,2,3-triazoles. A detailed investigation of the elementary steps, intermediates, and transition states of the two organocatalyzed metal-free click reactions is supported by DFT calculations and H-1 NMR monitoring experiments, providing detailed profiles for both reaction mechanisms. Distortion-interaction activation-strain (DIAS) analysis was also employed to further elucidate the regioselectivity in both reactions. (AU)

• FAPESP's process: 14/15839-9 - Mechanistic studies of the 1,3-dipolar cycloaddition (3 +2) reaction between azides and alkylidene-malononitriles: a theoretical investigation
• Grantee: Túlio Jardini Aímola
• Support Opportunities: Scholarships in Brazil - Scientific Initiation
• FAPESP's process: 18/01211-9 - Theoretical study of the mechanism of cycloaddition (3 + 2) reactions involving enolates and azides
• Grantee: Attilio Chiavegatti Neto
• Support Opportunities: Scholarships in Brazil - Scientific Initiation
• FAPESP's process: 20/10246-0 - Nuclear magnetic resonance spectroscopy: from pulse sequences to structural assignments
• Grantee: Claudio Francisco Tormena
• Support Opportunities: Research Projects - Thematic Grants
• FAPESP's process: 14/50249-8 - Green chemistry: sustainable synthetic methods employing benign solvents, safer reagents, and bio-renewable feedstock
• Grantee: Arlene Gonçalves Corrêa
• Support Opportunities: Research Grants - Research Centers in Engineering Program
• FAPESP's process: 20/01255-6 - Application of statistical tools in catalysis for understanding and predicting organic reactions
• Grantee: Marco Antonio Barbosa Ferreira
• Support Opportunities: Regular Research Grants
• FAPESP's process: 16/24726-9 - Kinetic studies on cycloaddition reactions (3+2) in the preparation of substituted 1,2,3-triazoles
• Grantee: Kelly Cintra Soares
• Support Opportunities: Scholarships in Brazil - Scientific Initiation
• FAPESP's process: 20/13563-7 - Prediction and design of catalytic processes using statistical modeling
• Grantee: Attilio Chiavegatti Neto
• Support Opportunities: Scholarships in Brazil - Doctorate (Direct)