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Synlett 2015; 26(06): 827-833
DOI: 10.1055/s-0034-1380118
DOI: 10.1055/s-0034-1380118
letter
Multicomponent Syntheses to Alkene- and Alkyne-Functionalized Benzopyrans via Alkynylation and [4+2] Cyclization in One-Pot Process
Authors
Further Information
Publication History
Received: 17 November 2014
Accepted after revision: 27 December 2014
Publication Date:
10 February 2015 (online)
Abstract
A novel multicomponent synthesis was found to be an efficient and elegant approach to 2,4-difunctionalized benzopyrans. This sequence includes ZnMe2-promoted alkynylation of salicylaldehyde and ZnCl2-mediated [4+2] cyclization proceeding in sequence of a one-pot process, providing a series of benzopyrans with good diastereoselectivities and moderate yields (dr 20:1 to 4:1). These products are potential precursors and bioactive core skeletons of natural products.
Supporting Information
- Supporting information for this article is available online at http://dx.doi.org/10.1055/s-0034-1380118.
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- 22 General Procedure for the Syntheses of 1–14 N-Ts-Proline (15.8 mg, 0.0588 mmol) and Cu(OTf)2 (21.2 mg, 0.0588 mmol) were mixed in dry toluene (2.0 mL) under Ar atmosphere. Then, ZnMe2 in toluene (1.2 M, 3.06 mL) was added. After 10 min, terminal alkyne (2.94 mmol) was added; 2 h later, the solution was cooled to 0 °C and treated with substituted salicylaldehyde (0.735 mmol) and dissolved in toluene (2.0 mL). The resulting mixture was stirred at 40 °C for 12 h. After salicylaldehyde was disappeared (monitoring with TLC), the solution was opened to atmosphere, 4 Ǻ MS and functionalized 1,3-butadiene (3.675 mmol) was added. Then, 5 min later, ZnCl2·OEt2 (1 M, 1.10 mL, 1.10 mmol) was dropped. The mixture was stirred 12 h at 40 °C and filtered through short diatomite columns to afford the crude product. Further purification by flash column chromatography afforded the product. Selected Data for 1 A light yellow liquid (54% yield). 1H NMR (400 MHz, CDCl3): δ = 7.41–7.43 (m, 2 H), 7.27–7.29 (m, 3 H), 7.09 (d, 1 H, J = 2.4 Hz), 6.74–6.82 (m, 2 H), 6.06 (dd, 1 H, J = 10.8, 17.2 Hz), 5.35 (dd, 1 H, J = 0.8, 17.6 Hz), 5.14 (dd, 1 H, J = 0.8 Hz, 10.8 Hz), 4.10 (dd, 1 H, J = 6.0, 10.4 Hz), 3.76 (s, 3 H), 2.22 (dd, 1 H, J = 6.0, 13.6 Hz), 2.10 (dd, 1 H, J = 10.4, 13.6 Hz), 1.37 (s, 3 H). 13C NMR (100 MHz, CDCl3): δ = 153.4, 146.7, 142.5, 131.6, 128.2, 127.9, 123.4, 121.2, 118.1, 114.7, 113.5, 113.2, 90.5, 82.0, 75.6, 55.7, 38.5, 26.5, 23.6. IR: νmax = 3059, 2929, 2855, 2375, 2226, 2066, 1954, 1878, 1689, 1598, 1492, 1427, 1373, 1266, 1219, 1146, 1093, 1039, 927, 911, 812, 757, 692, 531, 485 cm–1. ESI-HRMS: m/z calcd: 305.1536 [M + H]+; found: 305.1529.