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DOI: 10.1055/s-0031-1289566
An Efficient Pyrrole Synthesis via Silaphenylmercuric Triflate Catalyzed Cyclization of Homopropargyl Azides
Publikationsverlauf
Publikationsdatum:
09. November 2011 (online)
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Abstract
A mixture of phenylmercuric acetate and trifluoromethanesulfonic acid or silica gel supported phenylmercuric trifluoromethanesulfonate (silaphenyl mercuric triflate) efficiently catalyzed the formation of pyrroles from homopropargyl azide derivatives. The reactions proceed using 20 mol% of the heterogeneous catalyst with yields of isolated pyrroles ranging from 74% to 99%.
Key words
cyclization - heterocycles - heterogeneous catalysis - azides - alkynes
- Supporting Information for this article is available online:
- Supporting Information
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References and Notes
When the cyclization reaction of 1 with Hg(OTf)2 was quenched using Et3N and NaCl at -20 ˚C, the formation of pyrrolic mercury chloride corresponds to 7 was confirmed by ¹H NMR spectroscopy. However, pyrrolic mercury chloride was unstable under acidic conditions. During column chromatography on silica gel pyrrolic mercury chloride decomposed into 2.
16
Preparation of
Silaphenylmercuric Triflate (10) and a Typical Experimental Procedure
for a Silaphenyl-mercuric Triflate Catalyzed Cyclization
To
a suspension of dried silaphenylmercuric acetate 9 (0.2 mmol/g,
500 mg, 0.1 mmol) in MeNO2 (5 mL) was added TfOH (17.4 µL,
0.2 mmol), and the mixture was stirred for 10 min at r.t. The filtered
residue was washed with MeNO2 (10 mL) and dried to give
silaphenylmercuric triflate 10. Next, MeNO2 (4
mL) and prepared 10 were added to a dried two-neck
flask. To the stirred suspension of 10 was
added a solution of 1 (86 mg, 0.5 mmol)
in MeNO2 (1 mL) at r.t. under argon. The mixture was
stirred at r.t. for 5 min, and the catalyst was then removed by
filtration and washed with MeNO2 (10 mL). The combined
filtrates were concentrated under reduced pressure. Purification
by column chromatog-raphy on silica gel using hexane and EtOAc (10:1)
gave pyrrole 2 (70 mg, 97%).
In all cases (Table [³] ), recovery of 10 was between 99.29% and 99.89%.