TY - JOUR
T1 - Suppressing the anionic fries rearrangement of aryl dialkylcarbamates; the isolation of a crystalline ortho-deprotonated carbamate
AU - García, Felipe
AU - McPartlin, Mary
AU - Morey, James V.
AU - Nobuto, Daisuke
AU - Kondo, Yoshinori
AU - Naka, Hiroshi
AU - Uchiyama, Masanobu
AU - Wheatley, Andrew E.H.
PY - 2008/2/12
Y1 - 2008/2/12
N2 - In the presence of organolithium bases phenyl dialkylcarbamates have previously been shown to undergo facile rearrangement to yield the corresponding salicylamides. However, heterometallic lithium diethyl(2,2,6,6- tetramethylpiperidido)zincate achieves the clean directed ortho-metallation (DoM) of phenyl dialkylcarbamates, with [C6H4{OC(O)- NMe2}{Zn(μ-TMP)Et}Li]2 having been structurally characterized. DFT studies point to a stepwise deprotonative mechanism in which the zincate reagent exhibits kinetic amido basicity.
AB - In the presence of organolithium bases phenyl dialkylcarbamates have previously been shown to undergo facile rearrangement to yield the corresponding salicylamides. However, heterometallic lithium diethyl(2,2,6,6- tetramethylpiperidido)zincate achieves the clean directed ortho-metallation (DoM) of phenyl dialkylcarbamates, with [C6H4{OC(O)- NMe2}{Zn(μ-TMP)Et}Li]2 having been structurally characterized. DFT studies point to a stepwise deprotonative mechanism in which the zincate reagent exhibits kinetic amido basicity.
KW - Carbamates
KW - Directed ortho-metalation
KW - Lithium
KW - Zincates
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U2 - 10.1002/ejoc.200701096
DO - 10.1002/ejoc.200701096
M3 - Article
AN - SCOPUS:38949194950
SN - 0075-4617
SP - 644
EP - 647
JO - Justus Liebigs Annalen der Chemie
JF - Justus Liebigs Annalen der Chemie
IS - 4
ER -