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A Joint Experimental–Computational Comparative Study of the Pd 0 ‐Catalysed Reactions of Aryl Iodides and Aldehydes with N, O, and S Tethers
Author(s) -
Solé Daniel,
Mariani Francesco,
Fernández Israel
Publication year - 2015
Publication title -
european journal of organic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.825
H-Index - 155
eISSN - 1099-0690
pISSN - 1434-193X
DOI - 10.1002/ejoc.201500393
Subject(s) - heteroatom , chemistry , aryl , deprotonation , sulfur , nucleophile , intramolecular force , palladium , medicinal chemistry , metalation , photochemistry , organic chemistry , ring (chemistry) , catalysis , ion , alkyl
Abstract The influence of the heteroatom (nitrogen, oxygen, and sulfur) on the course of the palladium‐catalysed intramolecular reactions of aryl iodides and aldehydes having heteroatom‐containing tethers has been explored by an extensive experimental–computational (DFT) study. Two series of substrates were considered, namely aldehydes bearing either the α‐(2‐iodobenzylheteroatom) or β‐(2‐iodophenylheteroatom) moieties. While some experimental differences were observed when changing from nitrogen to oxygen or sulfur in the 2‐iodobenzyl series, the aldehydes in which the heteroatom is directly bonded to the aromatic ring showed common chemical behaviour regardless of the nature of the heteroatom. The different reaction pathways leading to the experimentally observed reaction products were studied by computational means. Our calculations suggest that in all cases the initial nucleophilic addition involving a σ‐aryl–Pd II intermediate is preferred over the competing concerted metallation–deprotonation (CMD) process.