Supplementary Material for Chemical Communications
This journal is © The Royal Society of Chemistry 2002
Supplementary data
The First Cobalt Catalyzed [2+2+2] Alkyne Cyclotrimerization in Aqueous
Medium at Room Temperature
Li Yong, Holger Butenchön
Institut für Organische Chemie, Universität Hannover
Schneiderberg 1B, D-30167 Hannover, Germany, Fax: +49/(0)511/762-4616
E-mail: holger.butenschoen@mbox.oci.uni-hannover.de
Experimental section:
All reactions were performed in an argon atmosphere using the Schlenk technique. (Di-tertbutylphosphanyl-P-ethyl)cyclopentadienylcobalt(I) (1) was prepared according to the published
procedure.1 The alkynes and solvents, which were purchased from Fluka, Aldrich, were
degassed and used without further purification. Column chromatography was performed on
Macherey and Nagel M 60 silica gel (40-63 µm). NMR: Bruker AVS 200 (1H: 200.1MHz, 13C:
50 MHz). – MS: Hewlett Packard 5898B (at 70 eV). – HRMS: Varian MAT 311.
General procedure (GP):
To a 20 ml Schlenk flask, 0.05 mmol (16.2 mg, 5 mol%) of catalyst 1, 1.00 mmol of alkyne, and
5 ml of degassed ethanol/water (20:80). The reaction mixture was stirred at room temperature
for 6-8 hours (for the internal alkynes at 60oC). Then the reaction mixture was exacted with
petroleum ether (3 x 20 ml). The combined organic layers were dried (MgSO4), filtered, and
concentrated in vacuo. The residue was purified by flash column chromatography (petroleum
ether or petroleum ether/ethyl acetate 40:1). Known arenes obtained were identified
spectroscopically by comparison with their published data (MS, NMR). The isomeric ratio was
determined by GC-MS of the crude product.
Study of the effect of catalyst amount on the reaction:
10 mol% of catalyst: GP, 0.10 mmol (32.4 mg ) of catalyst 1, 102 mg (0.11 ml, 1.00 mmol) of
phenylactylene (2a). 88 mg ( 0.29 mmol, 86 %) of 3a/4a (66:34).
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Supplementary Material for Chemical Communications
This journal is © The Royal Society of Chemistry 2002
2 mol% of catalyst: GP, 0.02 mmol (6.5 mg) of catalyst 1, 102 mg (0.11 ml, 1.00 mmol) of
phenylactylene (2a). 75 mg (0.25 mmol, 74%) of 3a/4a (69:31).
3a/4a: GP, 102 mg (0.11 mL, 1.00 mmol) of phenylactylene (2a), 86 mg (0.28 mmol, 84 %) of
3a/4a (69:31). Identified spectroscopically (1H NMR, MS) by comparison with literature data.2,3
3b/4b: GP, 82 mg (0.12 mL, 1.00 mmol) of 1-hexyne (2b), 76 mg (0.31 mmol, 93 %) of 3b/4b
(65:35). Identified spectroscopically (1H NMR, MS) by comparison with literature data.2,4
3c/4c: GP, 82 mg (0.12 mL, 1.00 mmol) of tert-butylactylene (2c), 61 mg (0.25 mmol, 74 %) of
3c/4c (73:27). Identified spectroscopically (1H NMR, MS) by comparison with literature
data.2,5,6
3d/4d: GP, 112 mg (2.00 mmol) of propargyl alcohol (2d), 7 ml of degassed ethanol/water
(20:80), 100 mg (0.59 mmol, 89 %) of 3d/4d (59:41). Identified spectroscopically (1H NMR,
MS) by comparison with literature data.7
3e/4e: GP. 98 mg (1.00 mmol) of ethyl propionate (2e), 70 mg (0.24 mmol, 71 %) of 3e/4e
(59:41). Identified spectroscopically (1H NMR, MS) by comparison with literature data.8,9
3f/4f: 102 mg (1.00 mmol) of 5-chloro-1-pentyne (2f), 78 mg (0.25 mmol, 77 %) of 3f/4f (76:24).
- 1H NMR (200 MHz, 300K, CDCl3): = 7.15-7.51 (m, 3H, Ph), 3.57-3.69 (m, 6H, Ph-CH2),
1.99-2.03 (m, 6H, CH2), 0.89-1.19 (m, 6H, CH2). – MS (70 eV), m/z (%): 306(100, M+). HRMS
calcd. for C15H21Cl3 306.0709, found: 306.0711.
3g/4g: GP, 166 mg (1.00 mmol) of 1-dodecyne, 151 mg (0.30 mmol, 91 %) of 3g/4g (77:23). -1H
NMR (200 MHz, 300K, CDCl3): = 7.21-6.81 (m, 3H, Ph), 2.53-2.56 (m, 6H, PhCH2), 2.132.21 (m, 6H, CH2), 2.01-2.07 (m, 6H, CH2). 1.41-1.63 (m, 36H, CH2), 0.88-0.93 (m, 9H, CH3). –
MS (70 eV), m/z (%): 498 (100, M+). - HRMS calcd. for C36H66 498.5165, found: 498.5169.
3h/4h: 116 mg (1.00 mmol) of para-tolylethyne (2h), 94 mg (0.27 mmol, 81 %) of 3h/4h
(57:43). Identified spectroscopically (1H NMR, MS) by comparison with literature data.10,11
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Supplementary Material for Chemical Communications
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5: GP, 110 mg (1.00 mmol) of diisopropylethyne, 56 mg (0.17 mmol, 51 %) of 3i. Identified
spectroscopically (1H NMR, MS) by comparison with literature data.12,13
6: GP, 178 mg (1.00 mmol) of diphenylethyne, 84 mg (0.16 mmol, 47 %) of 6. Identified
spectroscopically (1H NMR, MS) by comparison with literature data.10,12,14
7: GP, 106 mg (1.00 mmol) of 1,7-octadiyne, 102 mg (1.00 mmol) of phenylethyne (2a) 91 mg
(0.44 mmol, 44 %) of 7. Identified spectroscopically (1H NMR, MS) by comparison with
literature data.12,15
8: GP, 106 mg (1.00 mmol) of 1,7-octadiyne, 98 mg (1.00 mmol) of ethyl propionate (2e), 82 mg
(0.40 mmol, 40 %) of 8. Identified spectroscopically (1H NMR, MS) by comparison with
literature data.15
9: GP, 106 mg (1.00 mmol) of 1,7-octadiyne, 41 mg (1.00 mmol) of acetonitrile, 94 mg (64 %)
of 9. Identified spectroscopically (1H NMR, MS) by comparison with literature data.16,17
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Supplementary Material for Chemical Communications
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