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Synlett 2010(9): 1421-1425  
DOI: 10.1055/s-0029-1219835
LETTER
© Georg Thieme Verlag Stuttgart ˙ New York

Oxo-Diels-Alder Reaction of Danishefsky’s Diene with Aldehydes, Catalyzed by Chiral Tridentate Chromium(III)-Schiff Base Complexes

Sawomir Mięsowicza, Wojciech Chaładaja, Janusz Jurczak*a,b
a Institute of Organic Chemistry, Polish Academy of Sciences, 01-224 Warsaw, Poland
b Department of Chemistry, University of Warsaw, 02-093 Warsaw, Poland
Fax: +48(22)6326681; e-Mail: jurczak@icho.edu.pl;
Further Information

Publication History

Received 12 February 2010
Publication Date:
20 April 2010 (online)

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Abstract

The enantioselective hetero-Diels-Alder reaction of Danishefsky’s diene with simple aromatic and aliphatic aldehydes is catalyzed by chiral tridentate Schiff base-chromium(III) complexes. In many cases, 2,3-dihydropyran-4-ones are obtained in good yields (up to 99%) and high enantioselectivities (up to 97%).

Key words

Diels-Alder reaction - tridentate Schiff base chromium(III) complexes - 2,3-dihydropyran-4-ones - Danishefsky’s diene - enantioselective catalysis

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9

Typical procedure: Catalyst 2b (5.4 mg, 1 mol%) and a magnetic stirring bar was placed in a Schlenk tube and the atmosphere was replaced with argon. Under a gentle stream of argon, EtOAc (0.5 mL) was added. After dissolving the catalyst, the mixture was heated at 50 ˚C for 30 min, followed by addition of a freshly distilled aldehyde (4; 0.5 mmol) and then Danishefsky’s diene (3; 110 µL, 0.6 mmol) under a gentle stream of argon. The reaction was carried out at 50 ˚C for 12 h. After that time, the reaction mixture was cooled to r.t. and quenched with TFA (3 drops). After 30 min, the reaction mixture was diluted with CH2Cl2 and extracted with sat. aq K2CO3, H2O, and brine. The organic phase was concentrated and purified by chromatography over silica gel.

11

¹H NMR (200 MHz, CDCl3): δ = 2.6 (dd, J = 8.6, 3.8 Hz, 2 H), 2.75 (dd, J = 15, 3 Hz, 2 H), 3.6 (s, 3 H), 4.7 (m, 1 H), 4.7 (dd, J = 5.6, 2.2 Hz, 1 H), 7.4 (m, 5 H); ¹³C NMR (50 MHz, CDCl3): δ = 47.6, 48.6, 56.6, 73.2, 101.2, 125.7, 128.1, 128.6, 140.0, 204.9; IR: 2848, 1722, 1460, 1391, 1276, 1135, 1045, 762, 700, 460 cm-¹; MS: m/z [M + Na + MeOH]+ calcd: 261.11094; found: 261.10973 (in the presence of EtOH instead of MeOH, the observed ion was [M + Na + EtOH]+: calcd 275.12403; found: 275.12538); Anal. Calcd for C12H14O3: C, 69.88; H, 6.84; O, 23.27. Found: C, 69.93; H, 6.91; O, 23.16.