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Synlett 2015; 26(13): 1880-1884
DOI: 10.1055/s-0034-1380426
DOI: 10.1055/s-0034-1380426
letter
Copper-Catalyzed Regiospecific and 1,2-Regioselective Cyclopropanation of (1Z)-1-Amino- and (1Z)-1-Oxy-1,3-butadienyl Derivatives
Further Information
Publication History
Received: 16 April 2015
Accepted after revision: 13 May 2015
Publication Date:
09 July 2015 (online)
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Abstract
The copper-catalyzed regiospecific and 1,2-regioselective cyclopropanation of (1Z)-1-amino- and (1Z)-1-oxy-1,3-butadienyl derivatives, which could be prepared by Z-stereoselective 1,4-elimination with α-aryl diazoesters was successfully demonstrated. This successful regiospecific protocol enabled the preparation of the corresponding 1-amino- and 1-oxy-2-vinylcyclopropane derivatives as almost single stereoisomers.
Key words
cycloaddition - diastereoselectivity - diazo compounds - regioselectivity - stereoselective synthesisSupporting Information
- Supporting information for this article is available online at http://dx.doi.org/10.1055/s-0034-1380426.
- Supporting Information
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References and Notes
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- 15 Representative Procedure A solution of (Z)-1e (65 mg, 0.33 mmol) and 2a (77 mg, 0.30 mmol) in CH2Cl2 (3.0 mL) was added to (MeCN)4CuPF6 (2 mg, 0.005 mmol) in a flask at r.t. and stirred for 2 h under an argon atmosphere. Extractive workup and purification of the residue by chromatography on silica gel (CH2Cl2–MeOH = 200:1 to 40:1 as the eluent) afforded a mixture of (E)-3ea and 4ea [103 mg, (E)-3ea/4ea = 5:95; (E)-3ea, 4% yield; 4ea, 77% yield] as a white solid. Analytical Data of 4ea IR (KBr): 2982, 2935, 2873, 1728, 1711, 1693, 1490, 1479, 1447, 1369, 1317, 1294, 1250, 1209, 1188, 1156, 1128, 1077, 1066, 1011, 974, 920, 900, 827, 772, 762, 732 cm–1. 1H NMR (400 MHz, CDCl3): δ = 7.43 (2 H, ddd, J = 8.4, 2.2, 2.2 Hz, ArH), 7.15 (2 H, ddd, J = 8.4, 2.2, 2.2 Hz, ArH), 5.50–5.40 (1 H, m, CH=CH2), 5.31–5.18 (2 H, m, CH=CH 2), 4.95 (1 H, d, J = 7.2 Hz, 2-H), 3.90 [1 H, br, CH(CH3)2], 3.61 (3 H, s, OCH3), 3.59–3.47 [1 H, m, CH(CH3)2], 2.89–2.77 (1 H, m, 3-H), 1.40–1.10 [6 H, m, CH(CH 3)2], 0.89 [3 H, d, J = 6.4 Hz, CH(CH 3)2], 0.82 [3 H, d, J = 6.4 Hz, CH(CH 3)2]. 13C NMR (100 MHz, CDCl3): δ = 171.9, 154.1, 134.2, 131.11, 131.08, 130.7, 121.7, 119.0, 60.6, 60.5, 52.7, 46.4, 46.0, 36.6, 33.9, 20.7, 20.6, 20.5, 20.3. ESI-HRMS: m/z [M + H]+ calcd for C20H27BrNO4: 424.1118; found: 424.1111.
- 16 A study on decomposition of α-aryl diazoesters with rhodium(II) catalysts: Qu Z, Shi W, Wang J. J. Org. Chem. 2001; 66: 8139
Reviews:
Representative examples of cyclopropanation of dienyl derivatives:
Representative examples of cyclopropanation of 1-substituted 1,3-butadienyl derivatives:
Z-Regioselective cyclopropanation of E,Z-dienyl derivatives:
Preparation of 1-amino-2-vinyl (alkenyl) cyclopropanes:
Representative examples of preparation of 1-amino-2-vinylcyclopropane-1-carboxylic acid derivatives:
Preparation of 1-oxy-2-vinyl (alkenyl) cyclopropanes: