Synthesis of Cyclohexa-1,3-dienamines by Formal [3+3] Cycloaddition

Valérie Toum; Gérard Lhommet; Luc Dechoux

doi:10.1055/s-0032-1316987

Synlett, Inhaltsverzeichnis

Synlett 2012; 23(16): 2349-2352
DOI: 10.1055/s-0032-1316987

letter

Synthesis of Cyclohexa-1,3-dienamines by Formal [3+3] Cycloaddition

Authors

Valérie Toum

Université Pierre et Marie Curie Paris 6, Institut Parisien de Chimie Moléculaire, UMR CNRS 7201, 4 place Jussieu, case courrier 43, 75005 Paris, France, Fax: +33(1)44275079 eMail: luc.dechoux@upmc.fr
Gérard Lhommet

Université Pierre et Marie Curie Paris 6, Institut Parisien de Chimie Moléculaire, UMR CNRS 7201, 4 place Jussieu, case courrier 43, 75005 Paris, France, Fax: +33(1)44275079 eMail: luc.dechoux@upmc.fr
Luc Dechoux*

Université Pierre et Marie Curie Paris 6, Institut Parisien de Chimie Moléculaire, UMR CNRS 7201, 4 place Jussieu, case courrier 43, 75005 Paris, France, Fax: +33(1)44275079 eMail: luc.dechoux@upmc.fr

Abstract

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Abstract

Formal [3+3] cycloadditions of β-carboxymethylenamino esters with acrolein derivatives give a range of cyclohexa-2,6-dicarboxymethyl-1,3-dienamines that are potential acceptor–donor–acceptor systems.

Key words

multicomponent reactions - cyclohexa-1,3-dienamines - [3+3] cycloaddition - donor–acceptor systems

Volltext

Referenzen

References and Notes

1a Alladoum J, Dechoux L. Tetrahedron Lett. 2005; 46: 8203
1b Toum V, Kadouri-Puchot C, Hamon L, Lhommet G, Mouries-Mansuy V, Vanucci-Bacqué C, Dechoux L. Synthesis 2011; 2781

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For recent papers concerning the synthesis of 2,6,6-tricyanocyclohexa-1,3-dienamines, see:

3a Dyachenko VD, Rusanov EB. Russ. J. Org. Chem. 2006; 42: 1374
3b Wang XS, Zhang MM, Li Q, Yao CS, Tu SJ. Tetrahedron 2007; 63: 5265
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4 For a review, see: Kurreck H, Huber M. Angew. Chem. Int. Ed. Engl. 1995; 34: 849
5 For a review, see: Long NJ. Angew. Chem. Int. Ed. Engl. 1995; 34: 21
6 In all experiments we obtained about 120% of the expected weight

For recent publications concerning the synthesis of 2-hydroxytetrahydropyridines, see:

7a Ohba M, Natsutani I. Tetrahedron 2007; 63: 12689
7b Shen L, Cao S, Wu J, Li H, Zhang J, Wu M, Qian X. Tetrahedron Lett. 2010; 51: 4866
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8 Typical Procedure: To a solution of dimethyl 3-benzyl-aminopent-2-enedioate (0.43 g, 1.6 mmol) in CH₂Cl₂ (7 mL) at 0 °C, was added aldehyde (0.11 mL, 1.6 mmol) and benzoic acid (0.020 g, 0.16 mmol) and the reaction mixture was stirred for 24 h. The mixture was poured into a solution of NaHCO₃, extracted with CH₂Cl₂, dried over anhydrous MgSO₄, and evaporated. The residue was purified by silica gel column chromatography to afford the cyclohexa-1,3-dienamine. Dimethyl 2-Benzylamino-cyclohexa-1,5-diene-1,3-dicarboxylate (7a). IR (NaCl): 3348, 1735, 1655, 1595, 1436, 1224, 697 cm^–1. ¹H NMR (250 MHz, CDCl₃): δ = 2.25 (ddt, J = 2.9, 6.9, 16.8 Hz, 1 H, CHH), 2.65 (ddd, J = 1.4, 6.3, 16.8 Hz, 1 H, CHH), 3.47 (dd, J = 1.4, 6.9 Hz, 1 H, CH₂CH), 3.57 (s, 3 H, CH₃), 3.67 (s, 3 H, CH₃), 4.45 (m, 2 H, HNCH ₂), 5.23 (ddd, J = 2.9, 6.3, 9.4 Hz, 1 H, CH), 6.44 (dd, J = 2.9, 9.4 Hz, 1 H, CH), 7.20–7.43 (m, 5 H, PhH), 9.71 (m, 1 H, NH). ¹³C NMR (62.5 MHz, CDCl₃): δ = 25.3, 40.0, 46.5, 50.2, 52.4, 92.9, 110.8, 124.5, 126.8, 127.5, 128.8, 137.7, 157.1, 168.8, 170.9. HRMS: m/z [M + Na]⁺ calcd for C₁₇H₁₉NO₄: 324.1212; found: 324.1206. Dimethyl 2-[(1R)-Phenylethylamino]cyclohexa-1,5-diene-1,3-dicarboxylate (7b); Diastereoisomer 1: IR (NaCl): 3367, 1736, 1655, 1592, 1449, 1241, 756, 700 cm^–1. ¹H NMR (250 MHz, CDCl₃): δ = 1.53 (d, J = 6.7 Hz, 3 H, CH₃), 1.96–2.08 (m, 1 H, CHH), 2.38–2.64 (m, 1 H, CHH), 3.24 (dd, J = 1.4, 6.8 Hz, 1 H, CH₂CH), 3.69 (s, 3 H, CH₃), 3.71 (s, 3 H, CH₃), 4.61–4.76 (m, 1 H, PhCH), 5.12–5.23 (m, 1 H, CH=CH), 6.42 (ddd, J = 3.1, 4.4, 9.7 Hz, 1 H, CH=CH), 7.21–7.33 (m, 5 H, PhH), 9.70 (d, J = 7.0 Hz, 1 H, NH). ¹³C NMR (62.5 MHz, CDCl₃): δ = 25.0, 26.4, 40.7, 50.7, 52.7, 53.1, 92.9, 110.4, 124.9, 126.1, 127.3, 128.7, 144.2, 156.7, 169.1, 171.2. Diastereoisomer 2: ¹H NMR (250 MHz, CDCl₃): δ = 1.53 (d, J = 6.7 Hz, 3 H, CH₃), 2.38–2.64 (m, 2 H, CH₂), 3.12 (s, 3 H, CH₃), 3.70 (s, 3 H, CH₃), 3.55 (dd, J = 1.8, 7.0 Hz, 1 H, CH₂CH), 4.61–4.76 (m, 1 H, PhCH), 5.12–5.23 (m, 1 H, CH=CH), 6.42 (ddd, J = 3.1, 4.4, 9.7 Hz, 1 H, CH=CH), 7.21–7.33 (m, 5 H, PhH), 9.85 (d, J = 7.0 Hz, 1 H, NH). ¹³C NMR (62.5 MHz, CDCl₃): δ = 25.2, 26.4, 40.2, 52.0, 52.8, 53.1, 93.2, 111.3, 124.5, 125.4, 127.4, 129.1, 144.1, 156.7, 169.1, 170.8. HRMS: m/z [M + Na]⁺ calcd for C₁₈H₂₁NO₄: 338.1368; found: 338.1363 Methyl 2-Benzylamino-5-methyl-cyclohexa-1,5-diene-1,3-dicarboxylate (7c): IR (NaCl): 3385, 1733, 1654, 1592, 1436, 1215, 757, 668 cm^–1. ¹H NMR (250 MHz, CDCl₃): δ = 1.79 (s, 3 H, CH₃), 2.29–2.52 (m, 2 H, CH₂), 3.75 (dd, J = 1.9, 6.4 Hz, 1 H, CHCO₂Me), 3.68 (s, 3 H, CH₃), 3.73 (s, 3 H, CO₂CH₃), 4.46–4.64 (m, 2 H, CH ₂Ph), 6.20 (s, 1 H, CH), 7.13–7.38 (m, 5 H, PhH), 9.51–9.60 (m, 1 H, NH). ¹³C NMR (62.5 MHz, CDCl₃): δ = 22.6, 30.3, 40.7, 46.7, 50.7, 52.6, 93.2, 118.3, 121.2, 126.9, 127.6, 128.9, 138.1, 155.5, 169.0, 171.3. HRMS: m/z [M + Na]⁺ calcd for C₁₈H₂₁NO₄: 338.1368; found: 338.1363. Dimethyl 2-Benzylamino-4-methyl-cyclohexa-1,5-diene-1,3-dicarboxylate (7d): IR (NaCl): 3389, 1731, 1659, 1601, 1437, 1215, 668 cm^–1. ¹H NMR (250 MHz, CDCl₃): δ = 0.83 (d, J = 7.2 Hz, 3 H, CH₃), 2.74–2.86 (m, 1 H, CHCH₃), 3.33 (s, 1 H, CHCO₂Me), 3.60 (s, 3 H, CO₂CH₃), 3.68 (s, 3 H, CO₂CH₃), 4.37–4.56 (m, 2 H, CH ₂Ph), 5.23 (dd, J = 5.6, 9.8 Hz, 1 H, CH), 6.37 (d, J = 9.8 Hz, 1 H, CH), 7.20–7.36 (m, 5 H, PhH), 9.73–9.84 (m, 1 H, NH). ¹³C NMR (62.5 MHz, CDCl₃): δ = 17.8, 30.9, 46.3, 46.9, 50.5, 52.4, 92.1, 116.8, 122.1, 126.9, 127.5, 128.7, 138.5, 155.5, 168.8, 170.7. HRMS: m/z [M + Na]⁺ calcd for C₁₈H₂₁NO₄: 338.1368; found: 338.1363. Dimethyl 2-Benzylamino-4-phenyl-cyclohexa-1,5-diene-1,3-dicarboxylate (7e): IR (NaCl): 3363, 1736, 1656, 1597, 1494, 1451, 1227, 699 cm^–1. ¹H NMR (250 MHz, CDCl₃): δ = 3.56–3.59 (m, 1 H, CHCO₂Me), 3.62 (s, 3 H, CH₃), 3.66 (s, 3 H, CH₃), 3.99 (d, J = 6.2 Hz, 1 H, CHPh), 4.19–4.37 (m, 2 H, CH ₂Ph), 5.32 (ddd, J = 0.6, 6.1, 9.7 Hz, 1 H, CH=CH), 6.64 (d, J = 9.7 Hz, 1 H, CH=CH), 6.76–7.17 (m, 10 H, PhH), 9.61–9.66 (m, 1 H, NH). ¹³C NMR (62.5 MHz, CDCl₃): δ = 41.4, 46.3, 48.4, 50.8, 53.0, 92.9, 113.6, 125.2, 126.5, 127.1, 127.3, 127.7, 128.7, 137.7, 140.1, 155.4, 168.9, 170.6. HRMS: m/z [M + Na]⁺ calcd for C₂₃H₂₃NO₄: 400.1525; found: 400.1519. Methyl 1-Benzyl-6-hydroxy-2-methoxycarbonylmethyl-1,4,5,6-tetrahydro-pyridine-3-carboxylate (8a): ¹H NMR (250 MHz, CDCl₃): δ = 1.68–1.87 (m, 1 H, OHHCCHH), 1.96–2.10 (m, 1 H, HOHCCHH), 2.33–2.47 (m, 1 H, CHH), 2.67–2.77 (m, 1 H, CHH), 3.58 (d, J = 17.4 Hz, 1 H, CHHCO₂Me), 3.66 (s, 3 H, CH₃), 3.68 (s, 3 H, CH₃), 4.28 (d, J = 17.4 Hz, 1 H, CHHCO₂Me), 4.60 (q, J = 17.8 Hz, 2 H, PhCH ₂), 4.80 (m, 1 H, CHOH), 7.13–7.37 (m, 5 H, PhH). ¹³C NMR (62.5 MHz, CDCl₃): δ = 17.4, 27.6, 35.4, 50.9, 52.4, 52.1, 80.1, 98.7, 125.9, 127.3, 129.1, 138.2, 148.2, 168.7, 171.3. HRMS: m/z [M + Na]⁺ calcd for C₁₇H₂₁NO₅: 342.1317; found: 342.1312