Hg(OTf)₂-Catalyzed Instantaneous Hydration of β- and δ-Hydroxy Internal Alkynes with Complete Regioselectivity

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.

Hg(OTf)₂ - homogeneous catalysis - hydroxy internal alkyne - regioselectivity - neighboring-group effects

References and Notes

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Present address: Division of Chemistry, Graduate School of Science, Hokkaido University, Kita-ku, Saporo 060-0810, Japan.

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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

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All new compounds were fully characterized by spectroscopic methods.