RSS-Feed abonnieren
DOI: 10.1055/s-0029-1218267
One-Pot Synthesis of 1,4-Disubstituted 1,2,3-Triazoles from Aldehydes and Amines
Publikationsverlauf
Publikationsdatum:
08. Oktober 2009 (online)
Abstract
A one-pot, three-step synthesis of 1,4-disubstituted 1,2,3-triazoles from aldehyde and amine has been developed by in situ transformation of aldehyde into alkyne, followed by diazo-transfer of amine into azide and subsequent cycloaddition. This procedure allowed the synthesis of fluorescent amino acid derivatives as well as glycoconjugate mimetics.
Key words
aldehydes - amines - cycloadditions - one-pot reaction - triazoles
- Supporting Information for this article is available online:
- Supporting Information
-
1a
Rostovtsev VV.Green LG.Fokin VV.Sharpless KB. Angew. Chem. Int. Ed. 2002, 41: 2596 -
1b
Tornoe CW.Christensen C.Meldal M. J. Org. Chem. 2002, 67: 3057 - Selected reviews:
-
2a
Bock VD.Hiemstra H.van Maarseveen JH. Eur. J. Org. Chem. 2006, 51 -
2b
Moses JE.Moorhouse AD. Chem. Soc. Rev. 2007, 36: 1249 -
2c
Lutz JF. Angew. Chem. Int. Ed. 2007, 46: 1018 -
2d
Tron GC.Pirali T.Billington RA.Canonico PL.Sorba G.Genazzani AA. Med. Res. Rev. 2008, 28: 278 -
2e
Moorhouse AD.Moses JE. ChemMedChem 2008, 3: 715 - 3
Angell YL.Burgess K. Chem. Soc. Rev. 2007, 36: 1674 - 4
Bräse S.Gil C.Knepper K.Zimmermann V. Angew. Chem. Int. Ed. 2005, 44: 5188 -
5a
Feldman AK.Colasson B.Fokin VV. Org. Lett. 2004, 6: 3897 -
5b
Appukkuttan P.Dehaen W.Fokin VV.Van der Eycken E. Org. Lett. 2004, 6: 4223 -
5c
Demaray JA.Thuener JE.Dawson MN.Sucheck SJ. Bioorg. Med. Chem. Lett. 2008, 18: 4868 -
5d
Dururgkar KA.Gonnade RG.Ramana CV. Tetrahedron 2009, 65: 3974 -
6a
Odlo K.Høydahl EA.Hansen TV. Tetrahedron Lett. 2007, 48: 2097 -
6b
Sudhir VS.Baig RBN.Chandrasekaran S. Eur. J. Org. Chem. 2008, 2423 -
6c
Kumar D.Patel G.Reddy VB. Synlett 2009, 399 - 7
Kumar D.Reddy VB.Varma RS. Tetrahedron Lett. 2009, 50: 2065 - 8
Tao C.-Z.Cui X.Li J.Liu A.-X.Liu L.Guo Q.-X. Tetrahedron Lett. 2007, 48: 3525 -
9a
Yadav JS.Reddy BVS.Reddy GM.Chary DN. Tetrahedron Lett. 2007, 48: 8773 -
9b
Kumaraswamy G.Ankamma K.Pitchaiah A. J. Org. Chem. 2007, 72: 9822 - 10
Sreedhar B.Reddy PS.Krishna VR. Tetrahedron Lett. 2007, 48: 5831 - 11
Yadav JS.Reddy BVS.Chary DN.Reddy ChS. Tetrahedron Lett. 2008, 49: 2649 - 12
Chittaboina S.Xie F.Wang Q. Tetrahedron Lett. 2005, 46: 2331 - 13
Beckmann HSG.Wittmann V. Org. Lett. 2007, 9: 1 - 14
Moorhouse AD.Moses JE. Synlett 2008, 2089 -
15a
Luvino D.Amalric C.Smietana M.Vasseur J.-J. Synlett 2007, 3037 -
15b
Baxendale IR.Ley SV.Mansfield AC.Smith CD. Angew. Chem. Int. Ed. 2009, 48: 4017 -
16a
Shi F.Waldo JP.Chen Y.Larock RC. Org. Lett. 2008, 10: 2409 -
16b
Campbell-Verduyn L.Elsinga PH.Mirfeizi L.Dierckx RA.Feringa BL. Org. Biomol. Chem. 2008, 6: 3461 - 17
Zhang F.Moses JE. Org. Lett. 2009, 11: 1587 -
18a
David O.Maisonneuve S.Xie J. Tetrahedron Lett. 2007, 48: 6527 -
18b
Maisonneuve S.Fang J.Xie J. Tetrahedron 2008, 64: 8716 -
18c
Lin L.Shen Q.Chen Q.-R.Xie J. Bioorg. Med. Chem. 2008, 16: 9757 -
18d
Cheng KG.Liu J.Liu XF.Li HL.Sun HB.Xie J. Carbohydr. Res. 2009, 344: 841 -
18e
Li C.Tang J.Xie J. Tetrahedron 2009, 65: 7935 -
19a
Müller S.Liepold B.Roth GJ.Bestmann HJ. Synlett 1996, 521 -
19b
Pietruszka J.Witt A. Synthesis 2006, 4266 -
20a
Alper PB.Hung S.-C.Wong C.-H. Tetrahedron Lett. 1996, 34: 6029 -
20b
Nyffeler PT.Liang C.-H.Koeller KM.Wong C.-H. J. Am. Chem. Soc. 2002, 124: 10773 - 21
Goddard-Borger ED.Stick RV. Org. Lett. 2007, 9: 3797 - 22 During the preparation of this manuscript,
Smith et al. published the one-pot synthesis of triazoles from amines
and alkynes with imidazole-1-sulfonyl azide hydrochloride as diazo-transfer
reagent:
Smith NM.Greaves MJ.Jewell R.Perry MWD.Stocks MJ.Stonehouse JP. Synlett 2009, 1391 -
23a
Bae I.Han H.Chang S. J. Am. Chem. Soc. 2005, 127: 2038 -
23b
Cho SH.Yoo EJ.Bae I.Chang S. J. Am. Chem. Soc. 2005, 127: 16046 -
23c
Yoo EJ.Bae I.Cho SH.Han H.Chang S. Org. Lett. 2006, 8: 1347 -
23d
Cassidy MP.Raushel J.Fokin VV. Angew. Chem. Int. Ed. 2006, 45: 3154 -
23e
Yoo EJ.Ahlquist M.Kim SH.Bae I.Fokin VV.Sharpless KB.Chang S. Angew. Chem. Int. Ed. 2007, 46: 1730 -
24a
Winnik FM. Chem. Rev. 1993, 93: 587 -
24b
Abreu AS.Castanheira EMS.Ferreira PMT.Monteiro LS.Pereira G.Queiroz M.-JRP. Eur. J. Org. Chem. 2008, 5697 - 25
Wang G.Bobkov GV.Mikhailov SN.Schepers G.Van Aerschot A.Rozenski J.Van der Auweraer M.Herdewijn P.De Feyter S. ChemBioChem 2009, 10: 1175 - 26
Xie J.Ménand M.Maisonneuve S.Métivier R. J. Org. Chem. 2007, 72: 5980 - 27
Angell Y.Burgess K. Angew. Chem. Int. Ed. 2007, 46: 3649 - 29
Dondoni A. Chem. Asian J. 2007, 2: 700 - 30
Xie J.Thellend A.Becker H.Vidal-Cros A. Carbohydr. Res. 2001, 334: 177
References and Notes
General Procedure
To
a solution of aldehyde (1 equiv) in a mixture MeOH-CH2Cl2 (4
mL/4 mL for 0.5 mmol of aldehyde) were added K2CO3 (4
equiv) and the Bestmann-Ohira reagent (1.8 equiv). The
mixture was stirred at r.t. until complete conversion of aldehyde
to alkyne (TLC monitoring -
6 h maximum). Amine
hydrochloride salt (1.2 equiv), CuSO5˙5H2O
(1.2 equiv) and the imidazole-1-sulfonyl azide (1.2 equiv) were
then added to the reaction mixture and stirred at r.t. to transform
the amine into the azide intermediate. Reaction was judged to be
complete when imidazole-1-sulfonyl azide spot disappeared on TLC
(4 h maximum). Finally, ascorbic acid (4 equiv) was added, and the
reaction was stirred at r.t. overnight. The mixture was filtered
through a pad of Celite, washed with MeOH, and the solvents evaporated
under vacuum. The residue was purified by column chromatography
on silica gel (40-63 µM) to afford the triazoyl
compound.
Analytical Data for Selected
Compounds
Compound 12: mp
191 ˚C; R
f
= 0.55
(EtOAc-cyclohexane = 1:1); [α]D -89.2
(c 0.48, CH2Cl2). ¹H
NMR (400 MHz, CDCl3): δ = 3.89 (s,
3 H), 5.37 (s, 2 H, CH2), 8.01-8.29 (m, 9 H),
8.67 (d, 1 H, J = 9.2
Hz). ¹³C NMR (100 MHz, CDCl3): δ = 51.0
(CH2), 53.3 (CH3), 124.3, 124.7, 125.0, 125.3, 126.2,
127.3, 127.5, 128.0, 128.4, 128.7 (CH), 131.0, 131.4, 131.5, 148.0,
166.9 (C). ESI-HRMS: m/z calcd
for C21H15N3NaO2: 364.1062;
found: 364.1057.
Compound 29:
mp 114 ˚C; R
f
= 0.48
(EtOAc); [α]D -35.2
(c 0.47, CH2Cl2). ¹H
NMR (400 MHz, CDCl3): δ = 1.31 (s,
3 H), 1.36 (s, 3 H), 1.45 (s, 3 H), 1.60 (s, 3 H), 1.83 (s, 3 H), 1.83-2.01
(m, 2 H), 3.52-3.53 (m, 1 H), 3.61-3.63 (m, 1
H), 3.67 (dd, 1 H, J = 6.4,
10.1 Hz), 3.90 (dd, 1 H, J = 7.4,
10.1 Hz), 3.95-3.97 (m, 1 H), 4.11-4.13 (m, 1
H), 4.25 (t, 1 H, J = 6.8
Hz), 4.37 (dd, 1 H, J = 2.8,
5.0 Hz), 4.39-4.51 (m, 6 H), 4.55-4.59 (m, 3 H),
4.70 (dd, 1 H, J = 2.3,
7.8 Hz), 5.19 (d, 1 H, J = 1.8
Hz), 5.60 (d, 1 H, J = 5.0
Hz), 6.60 (d, 1 H, J = 9.6
Hz), 7.20-7.33 (m, 15 H), 7.65 (s, 1 H). ¹³C
NMR (100 MHz, CDCl3): δ = 23.4, 24.3,
25.1, 26.1, 26.3 (CH3), 32.4, 46.9 (CH2),
47.8, 64.7, 65.3 (CH); 67.6 (CH2), 70.8, 70.9 (CH); 72.0,
72.3 (CH2), 72.7, 73.2 (CH), 73.4 (CH2), 74.2,
75.1, 77.3 (CH), 96.7 (CH), 109.0, 109.3 (C), 123.6, 127.8, 127.9,
128.6, 128.7 (CH), 137.3, 137.5, 138.2, 145.1, 170.0 (C). ESI-HRMS: m/z calcd for C44H54N4NaO10: 821.3738;
found: 821.3732.