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DOI: 10.1055/s-0028-1088153
Hg(OTf)2-Catalyzed Instantaneous Hydration of β- and δ-Hydroxy Internal Alkynes with Complete Regioselectivity
Publikationsverlauf
Publikationsdatum:
20. März 2009 (online)
Abstract
The hydration of β- and δ-hydroxy internal alkynes catalyzed by Hg(OTf)2 took place instantaneously to give ketones with complete regioselectivity under mild conditions, whereas the hydration of internal alkyne without hydroxy moiety was very slow and gave a mixture of ketones. If the hydroxy group is located more than five carbons from the triple bond it has no significant effect upon the hydration reaction.
Key words
Hg(OTf)2 - homogeneous catalysis - hydroxy internal alkyne - regioselectivity - neighboring-group effects
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References and Notes
Present address: Division of Chemistry, Graduate School of Science, Hokkaido University, Kita-ku, Saporo 060-0810, Japan.
19
Typical Experimental
Procedure
To a stirred mixture of dec-5-yn-1-ol (3, 280 mg, 2 mmol) and H2O (108
mg, 6 mmol) in MeCN (6.6 mL) was added a solution of Hg(OTf)2 (0.1
M MeCN soln, 0.2 mL, 0.02 mmol) at r.t., and the mixture was stirred
for 5 min at the same temperature. After addition of Et3N
(30 µL) and then brine (6 mL), the organic materials were
extracted with Et2O. Dried and concentrated extract was
subjected to a column chromatography on SiO2 using hexane
and EtOAc (2:1) as an eluent to give 1-hydroxydecan-5-one (4, 275 mg, 90% yield) as a colorless
oil.²0a
All new compounds were fully characterized by spectroscopic methods.