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DOI: 10.1055/s-2008-1077881
Hg(OTf)2-Catalyzed Cyclization of N-Tosylanilinoallylic Alcohols to 2-Vinylindolines
Publication History
Publication Date:
11 June 2008 (online)
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Abstract
The Hg(OTf)2-catalyzed cyclization of N-tosylanilinoallylic alcohols giving rise to vinyl-substituted indolines has been developed. The reaction takes place with a highly efficient catalytic turnover (up to 1000 times) under mild conditions. The hydroxyl group of the organomercuric intermediate is protonated by in situ formed TfOH generating an oxonium cation, which regenerates the catalyst after demercuration.
Key words
Hg(OTf)2 - N-tosylanilinoallylic alcohol cyclization - 2-vinylindoline - 2-vinylpyrrolidine - 2-vinylpiperidine
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References and Notes
Typical Experiment
Procedure: To a solution of 5 (20
mg, 0.063 mmol) in CH2Cl2 (0.6 mL) was added
mercury triflate (0.01 M solution in MeCN, 6.3 µL, 0.063 µmol)
at r.t., and the mixture was stirred for 24 h. After addition of
sat. NaHCO3 solution, the dried and concentrated residue
was subjected to a column chromatography on silica gel using hexane-EtOAc
(12:1) as eluent to give 6 (18.4 mg, 98%)
as a colorless powder; mp 111 ˚C. IR (neat): 3066, 1598,
1354, 1165 cm-¹. ¹H
NMR (300 MHz, CDCl3): δ = 7.65 (d, J = 8.1 Hz, 1 H), 7.57 (d, J = 8.1 Hz, 2 H), 7.21 (m, 1
H), 7.17 (d,
J = 8.1
Hz, 1 H), 7.01-7.07 (m, 2 H), 6.99 (dd, J = 0.9,
7.5 Hz, 1 H), 5.91 (ddd, J = 6.3,
10.2, 16.8 Hz, 1 H), 5.39 (dt,
J = 1.2,
16.8 Hz, 1 H), 5.15 (dt, J = 1.5,
10.2 Hz, 1 H), 4.74 (m, 1 H), 2.95 (dd, J = 9.9,
15.9 Hz, 1 H), 2.64 (dd, J = 3.3, 15.9
Hz, 1 H), 2.36 (s, 3 H). ¹³C NMR (75
MHz, CDCl3):
δ = 143.8, 141.4,
137.6, 135.3, 131.2, 129.5, 127.7, 127.1, 125.1, 124.5, 116.8, 115.7,
63.8, 34.9, 21.5. HRMS (EI):
m/z [M]+ calcd
for C17H19NO3S+:
299.0980; found: 299.0999.