The Enantioselective Diels-Alder Reaction of 1-Methoxybuta-1,3-diene with n-Butyl Glyoxylate Catalyzed by Jacobsen’s Chromium Complexes

Piotr Kwiatkowski; Monika Asztemborska; Janusz Jurczak

doi:10.1055/s-2004-829055

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Synlett 2004(10): 1755-1758
DOI: 10.1055/s-2004-829055

LETTER

The Enantioselective Diels-Alder Reaction of 1-Methoxybuta-1,3-diene with n-Butyl Glyoxylate Catalyzed by Jacobsen’s Chromium Complexes

Piotr Kwiatkowski^a, Monika Asztemborska^b, Janusz Jurczak*^a,c
^a Institute of Organic Chemistry, Polish Academy of Sciences, Kasprzaka 44/52, 01-224 Warsaw, Poland
^b Institute of Physical Chemistry, Polish Academy of Sciences, Kasprzaka 44/52, 01-224 Warsaw, Poland
^c Department of Chemistry, Warsaw University, Pasteura 1, 02-093 Warsaw, Poland
Fax: +48(22)6326681; e-Mail: jurczak@icho.edu.pl;

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Publication History

Received 25 March 2004
Publication Date:
01 July 2004 (online)

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Abstract

The hetero-Diels-Alder reaction of 1-methoxybuta-1,3-diene (1) with n-butyl glyoxylate (2), catalyzed by chiral chromium(III) complexes 4-6 (2 mol%), afforded the [4+2]cycloadducts 3 in good yields (up to 96%), diastereoselectivity (up to 86% de), and enantioselectivity (up to 88% ee). Our approach opens an easy access to the synthetically important 6-substituted 2-methoxy-5,6-dihydro-2H-pyrans of type 3.

Key words

asymmetric catalysis - chromium(III) - Diels-Alder reaction - salen complexes - stereoselectivity

References

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19

Selected Data for Cycloadducts 3. cis - n -Butyl 2-Methoxy-5,6-dihydro-2 H -pyran-6-carboxylate (cis -3): ¹H NMR: δ = 6.08-5.98 (m, 1 H), 5.73-5.65 (m, 1 H), 5.07-5.03 (m, 1 H), 4.41-4.35 (m, 1 H), 4.19 (t, J = 6.7 Hz, 1 H), 4.14 (t, J = 6.7 Hz, 1 H), 3.50 (s, 3 H), 2.57-2.24 (m, 2 H), 1.74-1.59 (m, 2 H), 1.49-1.31 (m, 2 H), 0.94 (t, J = 7.3 Hz, 3 H). ¹³C NMR: δ = 170.8 (C), 127.7 (CH), 126.2 (CH), 97.2 (CH), 69.6 (CH₃), 64.9 (CH₂), 55.5 (CH), 30.5 (CH₂), 26.1 (CH₂), 19.0 (CH₂), 13.6 (CH₃). HRMS: m/z calcd for C₁₁H₁₈O₄Na [M + Na]⁺: 237.1103. Found: 237.1108. GC (column β-dex 120): T = 140°C, t _R[(2R,6S)-3] = 39.7 min, t _R[(2S,6R)-3] = 40.7 min; bp 109 °C/3 Torr.
trans - n -Butyl 2-Methoxy-5,6-dihydro-2 H -pyran-6-carboxylate (trans -3): ¹H NMR: δ = 6.06-5.97 (m, 1 H), 5.80-5.72 (m, 1 H), 5.00-4.97 (m, 1 H), 4.53-4.45 (m, 1 H), 4.20 (t, J = 6.7 Hz, 1 H), 4.19 (t, J = 6.7 Hz, 1 H), 3.46 (s, 3 H), 2.35-2.27 (m, 2 H), 1.73-1.59 (m, 2 H), 1.48-1.30 (m, 2 H), 0.94 (t, J = 7.3 Hz, 3 H). ¹³C NMR: δ = 171.2 (C), 127.6 (CH), 125.4 (CH), 95.8 (CH), 65.7 (CH₃), 64.9 (CH₂), 55.5 (CH), 30.5 (CH₂), 27.4 (CH₂), 19.0 (CH₂), 13.6 (CH₃). HRMS: m/z calcd for C₁₁H₁₈O₄Na [M + Na]⁺: 237.1103. Found: 237.1018. GC (column β-dex 120): T = 140°C, t_R [(2S,6S)-3] = 34.6 min, t_R [(2R,6R)-3] = 35.6 min.