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DOI: 10.1055/s-0031-1289908
Regiospecific Synthesis of 3,4-Dihydrocoumarins via Substrate-Controlled [1,3]- or [3,3]-Sigmatropic Rearrangement
Publication History
Publication Date:
28 November 2011 (online)
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Abstract
A regiospecific synthesis of 3,4-dihydrocoumarin derivatives has been achieved involving tandem rearrangement-cyclization of (E)-2-(aryloxymethyl)alk-2-enoates catalyzed by a Pd/Cu bimetallic system. Unexpected substrate-controlled [1,3]- or [3,3]-sigmatropic rearrangement was observed in the transformations.
Key words
[1,3]-sigmatropic rearrangement - [3,3]-sigmatropic rearrangement - palladium/copper bimetallic catalyst - substrate-controlled selectivity - 3,4-dihydrocoumarin
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References and Notes
General Experimental
Procedure and Spectroscopic Data
Compound 1a (268.3 mg, 1.0 mmol), Pd(OAc)2 (11.2
mg, 0.05 mmol), Cu(OTf)2 (18.1 mg, 0.05 mmol), and DCE
(2 mL) were added to a 10 mL sealed vessel protected under Ar. Then
the reaction mixture was stirred under reflux conditions for 15
h. Upon completion of the reaction, the resulting mixture was diluted
with CH2Cl2 (10 mL) and filtered through Celite.
After evaporation of the solvent under vacuum, the residue was purified
by column chromatography on silica gel (200-300 mesh) using cyclohexane-EtOAc
(12:1) as eluent to give pure 2a (153.7 mg,
65%) as a white solid. ¹H NMR (CDCl3,
500 MHz): δ = 4.09 (d, J = 2.0
Hz, 2 H), 7.01-7.18 (m, 3 H), 7.35-7.57 (m, 6
H), 7.99 (t, J = 2.0
Hz, 1 H).