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34
A. Vasudevan, M. K. Verzal
LETTER
ments before and after the reactions were completed (7.1
and 6.0 respectively) did not indicate a significant in-
crease in acidity at the end of the reaction, though pH
measurements during the reaction were precluded due to
safety reasons. In the context of results observed in this
study, it is also not possible to discount localized acidity
at the interface of the glass vessels and the reaction medi-
um. Studies are underway to elucidate the mechanism and
expand the scope of hydrations, which can be performed
(10) (a) Raner, R. D.; Strauss, C. R.; Vyskoc, F.; Mokbel, L. J.
Org. Chem. 1993, 58, 950. (b) Galema, S. A. Chem. Soc.
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Ortiz, A.; Diez-Barra, E. Contemp. Org. Synth. 1997, 4,
373. (d) Larhead, M.; Hallberg, A. Drug Discovery Today
2001, 6, 406.
(
11) (a) Breslow, R. Water as a Benign Solvent for Chemical
Reactions, In Green Chemistry; Oxford Press: , 1998, 225–
233. (b) Li, C. J. Water as a Benign Solvent for Chemical
Syntheses, In Green Chemistry; Oxford Press: , 1998, 234–
249. (c) Bagnell, L.; Cablewski, T.; Strauss, C. R.; Trainor,
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1
9
in superheated water.
(
(
12) Savage, P. E. Chem. Rev. 1999, 99, 603.
13) Gabriel, C.; Gabriel, S.; Grant, E. H.; Halstead, B. S. J.;
Mingos, D. P. M. Chem. Soc. Rev. 1998, 27, 213.
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(19) (a) Typical Procedure for the Hydration of Alkynes: A
suspension of the alkyne in a mixture of the alkyne (0.1 mol)
and 3 mL water in a sealed reaction vial was heated at 200 °C
6) Lucey, D. W.; Atwood, J. D. Organometallics 2002, 21,
®
2481.
in an Emrys synthesizer for 20 min, following which the
7) (a) Gedye, R.; Smith, F.; Westaway, K.; Ali, H.; Baldisera,
sample was cooled using compressed air. The product
usually separated from the water on standing or could be
extracted using 3 mL diethyl ether to afford the desired
ketones in yields described in Table 2, which demonstrated
purity and analytical data consistent with commercial
products. (b) Typical Procedure for the Hydroamination
of Alkynes: A mixture of the alkyne (0.87 mmol), amine
(0.87 mmol) and water (3 mL) in a sealed reaction vial was
L.; Laberge, L.; Rousell, J. Tetrahedron Lett. 1986, 27, 279.
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(8) Commercial vendors of microwave instrumentation
specifically for synthetic chemistry purposes include CEM
(www.cem.com), Milestone (www.milestonesci.com) and
Personal Chemistry (www.personalchemistry.com).
®
(
9) (a) Larhed, M.; Hallberg, A. J. Org. Chem. 1996, 61, 9582.
heated at 200 °C in an Emrys synthesizer for 20 min,
(
b) Strauss, C. R. Aust. J. Chem. 1999, 52, 83. (c) Wilson,
N. S.; Roth, G. P. Curr. Opin. Drug Discovery Dev. 2002, 5,
20. (d) Tan, K. L.; Vasudevan, A.; Bergman, R. G.; Ellman,
J. A.; Souers, A. J. Org. Lett. 2003, 5, 2131.
following which the sample was cooled using compressed
air. The product was extracted using diethyl ether (3 mL) to
afford 0.23 g of 12 (ref. 17).
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Synlett 2004, No. 4, 631–634 © Thieme Stuttgart · New York