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DOI: 10.1055/s-0029-1216744
A Procedure for Fast and Regioselective Copper-Free Click Chemistry at Room Temperature with p-Toluenesulfonyl Alkyne
Publikationsverlauf
Publikationsdatum:
04. Mai 2009 (online)
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Abstract
Sulfonyl alkyne group can undergo copper-free cyclization at room temperature with diverse azido compounds. In solvent-free conditions the reaction was fast, yielding 1,4-disubstituted regioisomers with high regioselectivity.
Key words
cycloadditions - regioselectivity - copper-free click chemistry - solvent-free reaction - p-toluenesulfonyl alkyne
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References and Notes
General Procedure
for the Copper-Free Cycloaddition
p-Toluenesulfonyl
alkyne 3 (31 mg, 171 µmol) and
8-azido-3,6-dioxaoctadecanol 4 (30 mg,
171 µmol) were dissolved in CH2Cl2 (1
mL). The solvent was evaporated under reduced pressure at 16 ˚C
(rotavapor, 20 mbar). Complete evap-oration was observed in less
than 5 min, and the stirring was continued under the same conditions
for 2 h. The residue was purified by flash chromatography on SiO2 (2:3
cyclohexane-EtOAc to EtOAc, then 39:1 EtOAc-MeOH)
to give 5a (45 mg, 74%) and 5b (4 mg, 6%) as colorless oils.
1-[8-Hydroxy-3,6-dioxaoctyl]-4-[
p
-toluenesulfonyl]-[1,2,3]-triazole
(5a)
¹H NMR (300 MHz, CDCl3): δ = 8.48
(1 H, s, CHTri), 7.91 (2 H, d, J = 8.5
Hz, arom. H), 7.30 (2 H, d, arom. H),
4.54 (2 H, t, J = 4.6 Hz, CH2CH2N),
3.80 (2 H, t, J = 4.8 Hz, CH2) 3.73
(2 H, t, J = 4.8 Hz, CH2),
3.58-3.53 (6 H, m, 3 × CH2), 2.37
(3 H, s, CH3). ¹³C NMR (75
MHz, CDCl3): δ = 149.0 (CqTri),
145.0 (CqAr), 137.2 (CqAr), 129.9 (CHAr), 128.1 (CHAr), 127.5 (CHTri),
72.7, 72.5, 70.4, 70.2, 68.6 (CH2), 61.7 (CH2OH),
50.1 (CH2N), 21.7 (CH3Ar). HRMS (ES+): m/z calcd for C15H21N3O5NaS:
378.1100; found: 378.1105.
1-[1′,2′:3′,4′-Di-
O
-isopropylidene-6-deoxy-α-
d
-galactopyranosid-6-yl]-4-[
p
-toluensulfonyl]-[1,2,3]-triazole
(18)
[α]D -58
(c 0.5, CH2Cl2). ¹H
NMR (300 MHz, CDCl3): δ = 8.31
(1 H, s, CHTri), 7.92 (2 H, d, J = 8.1
Hz, arom. H), 7.30 (2 H, d, J = 8.1 Hz, arom.
H), 5.50 (1 H, d, J
1,2 = 4.9
Hz, H-1), 4.64 (1 H, dd, J
5,6 = 3.7
Hz, J
6,6
′ = 14.0
Hz, H-6), 4.63 (1 H, dd, J
2,3 = 2.6
Hz, J
3,4 = 7.8 Hz,
H-3), 4.48 (1 H, dd,
J
5,6
′ = 8.5
Hz, H-6¢), 4.34 (1 H, dd, H-2),
4.18 (1 H, dd,
J
4,5 = 1.9
Hz, H-4), 4.12 (1 H, ddd, H-5), 2.40
(3 H, s, CH3), 1.52, 1.37, 1.34, 1.32 (12 H, 4 Ž s,
4 Ž isop. CH3). ¹³C
NMR (75 MHz, CDCl3): δ = 148.9
(CqTri), 145.0 (CqAr), 137.0 (CqAr), 129.9 (CHAr), 128.3 (CHAr),
127.2 (CHTri), 110.0 [C(CH3)2],
109.1 [C(CH3)2],
71.0, 70.3, 67.0, 66.7 (C-2,
C-3, C-4, C-5), 51.1 (C-6),
25.8, 24.9, 24.6 (CH3), 21.6 (CH3Ar). HRMS
(ES+): m/z calcd
for C21H27N3O7NaS: 488.1467;
found: 488.1474.