Abstract
The first example of a monocyano-substituted 2-carboxyimidazole
is reported. A synthesis of potassium 4-cyano-1-{[2-(trimethylsilyl)ethoxy]methyl}-1H -imidazole-2-carboxylate (2 ) is demonstrated where the carboxylate
group is introduced via bromine-magnesium exchange on a
SEM-protected cyanoimidazole followed by reaction with ethyl cyanoformate.
The synthesis includes the equilibration of a regioisomeric mixture
of SEM-protected imidazoles to give a single product.
Key words
cyanoimidazole - bromine-magnesium exchange - carboxylation - protecting group migration
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8 Accession number CCDC 694823. Crystal
data of 2 : C11 H16 KN3 O3 Si, M = 305.46
g mol-¹ , colorless plates. Monoclinic
space group P 21 /c , a = 20.8(4), b = 26.29(5), c = 11.52(2) Å, β = 96.24(3) ˚, V = 6263(2) ų , T = -180 ˚C, Z = 16, ρcalcd = 1.296
g cm-³ , µ (Cu-Kα) = 3.781,
multiscan, F (000) = 2560,
40580 reflections in h (-20/20), k (-13/26), l (-9/8) measured in
the range 2.72˚ ≤ θ ≤ 50.95˚, completeness
88%, 5979 unique reflections, R
int = 0.0987, 4703
reflections with F
o > 4σ,
693 parameters, 0 restraints, R 1obs = 0.1365, wR 2obs = 0.3996, R 1all = 0.1595, wR 2all = 0.3996,
GOOF = 1.544, largest difference peak
and hole 2.41/-0.97 eÅ-³ .