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  • Computational exploration of the copper(I)‐catalyzed conversion of hydrazones to dihalogenated vinyldiazene derivatives
Title: Computational exploration of the copper(I)‐catalyzed conversion of hydrazones to dihalogenated vinyldiazene derivatives
Abstract This computational study explores the copper (I) chloride catalyzed synthesis of (E)‐1‐(2,2‐dichloro‐1‐phenylvinyl)‐2‐phenyldiazene (2Cl‐VD) from readily available hydrazone derivative and carbon tetrachloride (CCl4).2Cl‐VDhas been extensively utilized to synthesize variety of heterocyclic organic compounds in mild conditions. The present computational investigations primarily focus on understanding the role of copper (I) andN1,N1,N2,N2‐tetramethylethane‐1,2‐diamine (TMEDA) in this reaction, TMEDA often being considered a proton scavenger by experimentalists. Considering TMEDA as a ligand significantly alters the energy barrier. In fact, it is only 8.3 kcal/mol higher compared to the ligand‐free (LF) route for the removal of a chlorine atom to form the radical·CCl3but the following steps are almost barrierless. This intermediate then participates in attacking the electrophilic carbon in the hydrazone. Crucially, the study reveals that the overall potential energy surface is thermodynamically favorable, and the theoretical turnover frequency (TOF) value is higher in the case of Cu(I)‐TMEDA complex catalyzed pathway.  more » « less
Award ID(s):
2152633
PAR ID:
10507940
Author(s) / Creator(s):
; ; ; ; ;
Publisher / Repository:
Wiley
Date Published:
Journal Name:
Journal of Computational Chemistry
ISSN:
0192-8651
Format(s):
Medium: X
Sponsoring Org:
National Science Foundation
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