Subscribe to RSS
DOI: 10.1055/s-0031-1289532
Gold-Catalyzed Cyclization of Oxo-1,5-enynes
Publication History
Publication Date:
19 October 2011 (online)
![](https://www.thieme-connect.de/media/synlett/201201/lookinside/thumbnails/10.1055-s-0031-1289532-1.jpg)
Abstract
Cationic gold(I) complexes catalyze the cycloisomerization of oxo-1,5-enynes to form oxatricyclic derivatives through an intramolecular Prins reaction.
Key words
gold - enynes - alkynes - cycloisomerization
- Supporting Information for this article is available online:
- Supporting Information
-
1a
Jiménez-Núñez E.Echavarren AM. Chem. Rev. 2008, 108: 3326 -
1b
Gorin DJ.Sherry BD.Toste FD. Chem. Rev. 2008, 108: 3351 -
1c
Michelet V.Toullec PY.Genêt JP. Angew. Chem. Int. Ed. 2008, 47: 4268 -
1d
Fürstner A. Chem. Soc. Rev. 2009, 38: 3208 - 2
Jiménez-Núñez E.Claverie CK.Nieto-Oberhuber C.Echavarren AM. Angew. Chem. Int. Ed. 2006, 45: 5451 - 3
Escribano-Cuesta A.López-Carrillo V.Janssen D.Echavarren AM. Chem. Eur. J. 2009, 11: 5646 -
4a
Schelwies M.Dempwolff AL.Rominger F.Helmchen G. Angew. Chem. Int. Ed. 2007, 46: 5598 -
4b
Schelwies M.Moser R.Dempwolff AL.Rominger F.Helmchen G. Chem. Eur. J. 2009, 15: 10888 - 5
Jiménez-Núñez E.Molawi K.Echavarren AM. Chem. Commun. 2009, 7327 - 6
Molawi K.Delpont N.Echavarren AM. Angew. Chem. Int. Ed. 2010, 49: 3517 - 7
Zhou Q.Chen X.Ma D. Angew. Chem. Int. Ed. 2010, 49: 3513 - 8
Zhang L.Sun J.Kozmin SA. Adv. Synth. Catal. 2006, 348: 2271 - 9
López-Carrillo V.Huguet N.Mosquera .Echavarren AM. Chem. Eur. J. 2011, ; in press; doi: 10.1002/chem.201101749 -
12a
Nieto-Oberhuber C.López S.Echavarren AM. J. Am. Chem. Soc. 2005, 127: 6178 -
12b
Herrero-Gómez E.Nieto-Oberhuber C.López S.Benet-Buchholz J.Echavarren AM. Angew. Chem. Int. Ed. 2006, 45: 5455 -
12c
Pérez-Galán P.Delpont N.Herrero-Gómez E.Maseras F.Echavarren AM. Chem. Eur. J. 2010, 16: 5324 - 13
Amijs CHM.López-Carrillo V.Raducan M.Pérez-Galán P.Ferrer C.Echavarren AM. J. Org. Chem. 2008, 73: 7721 - Recent reviews on NHC-Au complexes in catalysis, see:
-
14a
Nolan SP. Acc. Chem. Res. 2010, 44: 91 -
14b
Gaillard S.Nun P.Slawin AMZ.Nolan SP. Organometallics 2010, 29: 5402 -
15a
Eschenmoser A.Ruzicka L.Jeger O.Arigoni D. Helv. Chim. Acta 1955, 38: 1890 -
15b
Stork G.Burgstahler AW. J. Am. Chem. Soc. 1955, 77: 5068 -
15c
Eschenmoser A.Arigoni D. Helv. Chim. Acta 2005, 88: 3011 - Stepwise mechanisms might occur in the reactions catalyzed by cyclase enzymes, see:
-
16a
Lodeiro S.Xiong Q.Wilson WK.Kolesnikova MD.Onak CS.Matsuda SPT.
J. Am. Chem. Soc. 2007, 129: 11213 -
16b
Gao J.Ma S.Major DT.Nam K.Pu J.Truhlar DG. Chem. Rev. 2006, 106: 3188 -
16c
Yoder RA.Johnston JN. Chem. Rev. 2005, 105: 4730 -
17a
Fürstner A.Morency L. Angew. Chem. Int. Ed. 2008, 47: 5030 -
17b
Böhringer S.Gagosz F. Adv. Synth. Catal. 2008, 350: 2617 -
17c
Sethofer SG.Mayer T.Toste FD. J. Am. Chem. Soc. 2010, 132: 8276 -
17d
Toullec PY.Blarre T.Michellet V. Org. Lett. 2009, 11: 2888 -
18a
Nieto-Oberhuber C.Pérez-Galán P.Herrero-Gómez E.Lauterbach T.Rodríguez C.López S.Bour C.Rosellón A.Cárdenas DJ.Echavarren AM. J. Am. Chem. Soc. 2008, 130: 269 -
18b
Jiménez-Núñez E.Raducan M.Lauterbach T.Molawi K.Solorio CR.Echavarren AM. Angew. Chem. Int. Ed. 2009, 48: 6152 ; Angew. Chem. 2009, 121, 6268 -
18c
Pérez-Galán P.Martin NJA.Campaña AG.Cárdenas DJ.Echavarren AM. Chem. Asian J. 2011, 6: 482
References and Notes
(
E
)-4-Methyl-6-(phenylsulfonyl)non-4-en-8-ynal
(10a): Yellow solid; mp 52-54 ˚C. ¹H
NMR (400 MHz, CDCl3):
δ = 9.73
(t, J = 1.5 Hz, 1 H),
7.97-7.73 (m, 2 H), 7.69-7.60 (m, 1 H),
7.56-7.52 (m, 3 H), 5.08 (ddd, J = 10.3,
2.6, 1.3 Hz, 1 H), 3.95 (td, J = 10.2,
3.8 Hz, 1 H), 2.98 (ddd, J = 16.7,
3.8, 2.8 Hz, 1 H), 2.60 (ddd, J = 16.7,
10.2, 2.7 Hz, 2 H), 2.47 (tm, J = 7.5 Hz,
2 H), 2.32 (t, J = 7.4 Hz,
2 H), 1.94 (t, J = 2.7 Hz,
1 H), 1.32 (d, J = 1.3 Hz,
3 H). ¹³C NMR (CDCl3,
100 MHz): δ = 201.27 (CHO), 144.80 (C), 137.37 (C),
134.02 (C), 129.33 (CH), 129.28 (CH), 129.13 (CH), 116.85 (CH),
71.11 (CH), 63.03 (CH), 41.66 (CH2), 31.8 (CH2),
18.86 (CH2), 16.83 (CH3). IR (thin film):
3244 (CH terminal alkyne), 1712 (C=O) cm-¹.
HRMS (ESI): m/z [M + Na]+ calcd
for C16H18O3SNa: 313.0874; found:
313.0867. (
E
)-5-Methyl-7-(phenylsulfonyl)dec-5-en-9-yn-2-one (10b):
Yellow solid; mp 53-55 ˚C. ¹H
NMR (400 MHz, CDCl3): δ = 7.84-7.82
(m, 2 H), 7.65 (t, J = 7.4 Hz,
1 H), 7.56-7.52 (m, 2 H), 5.06 (dd, J = 10.3, 1.2 Hz, 1 H),
3.95 (td, J = 10.2, 3.8 Hz,
1 H), 2.99 (ddd, J = 16.7,
3.5, 2.9 Hz, 1 H), 2.61 (ddd, J = 16.7,
10.1, 2.6 Hz, 1 H), 2.48 (dd, J = 8.6, 6.6 Hz,
2 H), 2.27 (t, J = 7.8 Hz,
2 H), 2.15 (s, 3 H), 1.94 (t, J = 2.6 Hz,
1 H), 1.31 (d, J = 1.2 Hz,
3 H). ¹³C NMR (CDCl3, 100
MHz): δ = 207.58 (C), 145.43 (C), 137.36 (C),
133.93 (CH), 129.25 (CH), 129.05 (CH), 116.17 (CH), 79.00 (C), 71.02
(CH), 62.99 (CH), 41.52 (CH2), 33.25 (CH2),
30.05 (CH3), 18.82 (CH2), 16.86 (CH3).
IR (thin film): 3295 (CH terminal alkyne), 1704 (C=O) cm-¹.
HRMS (ESI): m/z [M + Na]+ calcd
for C17H20O3SNa: 327.1031; found:
327.1030
General procedure for the cyclization of oxo-1,5-enynes : 1,5-Oxoenyne and the gold(I) complex A-G (2-5 mol%) were dissolved in CH2Cl2 (0.5-1.2 mL) and stirred at room temperature until full conversion was observed (reaction monitored by TLC). One drop of Et3N was added and the crude reaction was filtered through Celite and the solvent was evaporated under reduced pressure. The residue was purified by column chromatography on silica gel to provide the cyclized product. (1 S ,3a S ,4 S ,7 R ,7a R )-7-Methyl-1-[(phenylperoxy)thio]-3a,4,5,6,7,7a-hexahydro-1 H -4,7-epoxyindene (11a): ¹H NMR (500 MHz, CDCl3): δ = 7.89-7.85 (m, 2 H), 7.75-7.62 (m, 1 H), 7.61-7.51 (m, 2 H), 5.99 (dt, J = 5.7, 2.0 Hz, 1 H), 5.77 (dt, J = 4.3, 1.9 Hz, 1 H), 4.48 (t, J = 5.6 Hz, 1 H), 4.00-3.98 (m, 1 H), 3.34-3.01 (m, 1 H), 2.74 (dt, J = 9.5, 2.0 Hz, 1 H), 1.73-1.51 (m, 1 H), 1.51-1.33 (m, 2 H), 1.27-1.25 (m, 1 H), 1.21 (s, 3 H). ¹³C NMR (CDCl3, 125 MHz): δ = 141.36 (CH), 136.91 (C), 133.97 (CH), 129.49 (CH), 129.12 (CH), 125.04 (CH), 86.01 (C), 79.03 (CH), 72.35 (CH), 56.03 (CH), 52.88 (CH), 30.32 (CH2), 28.58 (CH2), 20.18 (CH3). HRMS (ESI): m/z [M + Na]+ calcd for C16H18O3SNa: 313.0874; found: 313.0869. (1 S ,3a S ,4 R ,7 S ,7a R )-7-Methyl-1-[(phenylperoxy)thio]-3a,4,5,6,7,7a-hexahydro-1 H -4,7-epoxyindene (11a′): ¹H NMR (500 MHz, CDCl3): δ = 7.88-7.85 (m, 2 H), 7.73-7.60 (m, 1 H), 7.63-7.49 (m, 2 H), 5.92 (dt, J = 5.7, 2.2 Hz, 1 H), 5.62 (dt, J = 5.7, 2.1 Hz, 1 H), 4.26-4.18 (m, 1 H), 4.14 (d, J = 5.1 Hz, 1 H), 2.96 (ddd, J = 7.0, 4.6, 2.3 Hz, 1 H), 2.72 (dd, J = 7.2, 3.1 Hz, 1 H), 1.82-1.74 (m, 1 H), 1.62-1.58 (m, 1 H), 1.56-1.48 (m, 2 H), 1.32 (s, 3 H). ¹³C NMR (CDCl3, 125 MHz): δ = 139.30 (CH), 137.71 (C), 133.90 (CH), 129.23 (CH), 129.17 (CH), 126.02 (CH), 84.58 (C), 78.97 (CH), 74.25 (CH), 58.21 (CH), 50.34 (CH), 36.31 (CH2), 30.75 (CH2), 17.99 (CH3). HRMS (ESI): m/z [M + Na]+ calcd for C16H18O3SNa: 313.0874; found: 313.0882