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Stereoretentive Copper(II)‐Catalyzed Ritter Reactions of Secondary Cycloalkanols
Author(s) -
Alhuniti Mohammed H.,
Lepore Salvatore D.
Publication year - 2013
Publication title -
advanced synthesis and catalysis
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.541
H-Index - 155
eISSN - 1615-4169
pISSN - 1615-4150
DOI - 10.1002/adsc.201300233
Subject(s) - chemistry , ritter reaction , catalysis , aryl , trifluoromethanesulfonate , carbocation , thionyl chloride , medicinal chemistry , organic chemistry , amide , nucleophile , alkyl , copper , photochemistry , chloride
A Ritter‐like coupling reaction of cyclic alcohols and both aryl and alkyl nitriles to form amides catalyzed by copper(II) triflate is described. These reactions proceed in good yields under mild and often solvent‐free conditions. With 2‐ and 3‐substituted cycloalkanols, amide products are formed with near complete retention of configuration. This is likely due to fast nucleophilic capture of non‐planar carbocations (hyperconjomers) stabilized by ring hyperconjugation. A critical aspect of this novel catalytic cycle is the in situ activation of the alcohol substrates by thionyl chloride to form chlorosulfites.