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Synlett 2010(14): 2125-2129  
DOI: 10.1055/s-0030-1258522
LETTER
© Georg Thieme Verlag Stuttgart ˙ New York

Rearrangement of Pyran Derivatives Obtained from Vinyl Malononitriles and Aldehydes via Vinylogous Aldol Reaction: A Novel Facile Method for the Synthesis of Dienamides

Thelagathoti Hari Babu, Sujeet Pawar, D. Muralidharan, Paramasivan T. Perumal*
Organic Chemistry Division, Central Leather Research Institute (a CSIR Laboratory), Adyar, Chennai 600 020, India
Fax: +91(44)24911589; e-Mail: ptperumal@gmail.com;
Further Information

Publication History

Received 15 May 2010
Publication Date:
27 July 2010 (online)

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Abstract

A novel one-pot approach to a variety dienamides from vinyl malononitriles and aldehydes via vinylogous aldol reaction was achieved by the electrolytic ring opening of the initially formed pyran derivatives under mild basic catalysis with good diastereoselectivity.

Key words

vinyl malononitrile - vinylogous aldol reaction - pyran rearrangement - dienamides

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19

General Procedure for the Synthesis of Dienamide 3a
The mixture of vinyl malononitrile 1a (1.5 mmol), aldehyde 2a (1 mmol), and Et3N (1 mmol) in ethylene glycol (7 mL) was stirred at 40 ˚C for 40 min. After the reaction was complete as indicated by TLC, the reaction mixture was cooled to r.t. diluted with acid H2O (10 mL). The resulting precipitate was filtered and subjected to chromatographic purification over silica gel (Merck; 100-200 mesh; EtOAc-hexane = 3:7) to obtain dienamide 3a (78%) as a single diastereomer.
Spectral Data of Dienamide 3a (Table 1, Entry 1) Off-white solid; yield 78%; mp 392 ˚C. ¹H NMR (500 MHz, DMSO-d 6): δ = 1.55 (m, 2 H), 1.75 (m, 2 H), 2.53 (m, 4 H), 6.42 (s, 1 H), 7.21 (d, J = 8.4 Hz, 2 H), 7.38 (d, J = 8.4 Hz, 2 H), 7.53 (s, 1 H, D2O exchangeable), 7.87 (s, 1 H, D2O exchangeable). ¹³C NMR (125 MHz, DMSO-d 6): δ = 26.0, 26.4, 29.9, 35.1, 106.6, 116.8, 127.2, 128.9, 128.9, 130.1, 131.4, 132.6, 135.0, 139.3, 164.3, 164.5. IR (KBr): νmax = 3397, 3385, 2935, 2216, 1673, 1388, 1092, 626 cm-¹. ESI-MS: 287 [M + 1]. Anal. Calcd (%) for C16H15ClN2O: C, 67.02; H, 5.27; N, 9.77. Found: C, 66.97; H, 5.21; N, 9.71.
Spectral Data of Dienamide 3k (Table 1, Entry 11) Off-white solid; yield 80%; mp 364 ˚C. ¹H NMR (500 MHz, CDCl3): δ = 0.89 (t, J = 6.9 Hz, 3 H), 1.32 (m, 4 H), 1.47 (m, 2 H), 1.64 (m, 2 H), 2.82 (t, J = 8.4 Hz, 2 H), 5.87 (s, 1 H, D2O exchangeable), 6.33 (s, 1 H, D2O exchangeable), 7.17 (d, J = 16.9 Hz, 1 H), 7.69 (d, J = 8.4 Hz, 2 H), 8.22 (d, J = 8.4 Hz, 2 H), 8.58 (d, J = 16.1 Hz. 1 H). ¹³C NMR (125 MHz, CDCl3): δ = 14.1, 22.5, 29.5, 30.3, 31.4, 33.8, 105.6, 117.8, 124.2, 124.2, 128.0, 128.7, 128.7, 137.1, 141.9, 148.2, 163.1, 166.0. IR (KBr): νmax = 3358, 3187, 2930, 2217, 1670, 1600, 1521, 1338 cm-¹. ESI-MS: 328 [M + 1]. Anal. Calcd (%) for C18H21N3O3: C, 66.04; H, 6.47; N, 12.84. Found: C, 66.01; H, 6.43; N, 12.77.

20

Crystallographic data for compound 3a in this paper have been deposited with the Cambridge Crystallographic Data Centre as supplemental publication No. CCDC- 775677. Copies of the data can be obtained, free of charge on application to CCDC, 12 Union Road, Cambridge CB2 1EZ, UK [fax: +44 (1223)336033 or email: deposit@ccdc.cam.ac.uk].