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Preferential cross‐coupling of naphthol derivatives mediated by copper(II)
Author(s) -
Koščová Simona,
Roithová Jana,
Hodačová Jana
Publication year - 2013
Publication title -
journal of physical organic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.325
H-Index - 66
eISSN - 1099-1395
pISSN - 0894-3230
DOI - 10.1002/poc.3086
Subject(s) - chemistry , copper , deprotonation , substituent , density functional theory , fragmentation (computing) , computational chemistry , medicinal chemistry , stereochemistry , crystallography , organic chemistry , ion , computer science , operating system
Preferential cross‐coupling of differently N ‐substituted amides of 3‐hydroxy‐2‐naphthoic acids 1 and 2 catalyzed by Cu(OH)Cl•TMEDA was observed. The reaction mechanism was investigated using mass spectrometry tools. It was shown that the complexation properties of the N ‐substituent significantly influence the properties of the corresponding copper complexes of the deprotonated compounds ([(1‐H)Cu(TMEDA)] + and [(2‐H)Cu(TMEDA)] + ). Analysis of the fragmentation patterns of the copper complexes revealed that while the former is prone to the one electron oxidation of (1‐H)ˉ, the latter has a larger binding energy between (2‐H)ˉ and copper(II). Interplay between the abundance of the copper complexes and their reactivities explains the preferential cross‐coupling . The results are further supported by exploratory density functional theory calculations. Copyright © 2013 John Wiley & Sons, Ltd.