Efficient Regioselective Opening of Epoxides by Nucleophiles in Water under Simultaneous Ultrasound/Microwave Irradiation

Giovanni Palmisano; Silvia Tagliapietra; Alessandro Barge; Arianna Binello; Luisa Boffa; Giancarlo Cravotto

doi:10.1055/s-2007-984891

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Synlett 2007(13): 2041-2044
DOI: 10.1055/s-2007-984891

LETTER

Efficient Regioselective Opening of Epoxides by Nucleophiles in Water under Simultaneous Ultrasound/Microwave Irradiation

Giovanni Palmisano^a, Silvia Tagliapietra^b, Alessandro Barge^b, Arianna Binello^b, Luisa Boffa^b, Giancarlo Cravotto*^b
^a Dipartimento di Scienze Chimiche e Ambientali, Università degli Studi dell’Insubria, Via Valleggio 11, 22100 Como, Italy
^b Dipartimento di Scienza e Tecnologia del Farmaco, Università degli Studi di Torino, Via Giuria 9, 10235 Torino, Italy
Fax: +39(011)6707687; e-Mail: giancarlo.cravotto@unito.it;

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Publication History

Received 14 May 2007
Publication Date:
12 July 2007 (online)

Abstract
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Abstract

Epoxide cleavage by nucleophiles in aqueous media may suffer from competition by water itself, yielding the diol as byproduct. However, when the reaction was carried out under high-intensity ultrasound or microwaves, attack by the nucleophile was strongly promoted and water no longer reacted. Best results were achieved under simultaneous ultrasound/microwave irradiation: a series of mono-, di- and trisubstituted oxiranes reacted rapidly with sodium azide or 1-(3-chlorophenyl)piperazine, usually leading to the corresponding more substituted alcohols in acceptable to high yields. This catalyst-free, greener protocol achieves a much faster cleavage of epoxides with a high regioselectivity.

Key words

epoxide opening - ultrasound - microwave - reaction in water - one-pot reaction

References and Notes

1 Kolb HC. Finn MG. Sharpless KB. Angew. Chem. Int. Ed. 2001, 40: 2004

Crossref PubMed Search in Google Scholar
2 Sekar G. Singh VK. J. Org. Chem. 1999, 64: 287

Crossref PubMed Search in Google Scholar
3a Ollevier T. Lavie-Compin G. Tetrahedron Lett. 2004, 45: 49

Crossref PubMed Search in Google Scholar
3b Chakraborti AK. Kondaskar A. Tetrahedron Lett. 2003, 44: 8315

Crossref PubMed Search in Google Scholar
3c Fringuelli F. Pizzo F. Tortoioli S. Vaccaro L. J. Org. Chem. 2004, 69: 7745

Crossref PubMed Search in Google Scholar
3d Sekar G. Singh VK. J. Org. Chem. 1999, 64: 287

Crossref PubMed Search in Google Scholar
4 Fringuelli F. Piermatti O. Pizzo F. Vaccaio L. J. Org. Chem. 1999, 64: 6094

Crossref Search in Google Scholar
5a Mojtahedi MM. Saidi MR. Bolourtchian M. J. Chem. Res., Synop. 1999, 128

Crossref
5b Eshghi H. Rahimizadeh M. Shoryabi A. Synth. Commun. 2005, 35: 791

Crossref Search in Google Scholar
5c Rodríguez-Escrich S. Popa D. Jimeno C. Vidal-Ferran A. Pericàs MA. Org. Lett. 2005, 7: 3829

Crossref Search in Google Scholar
6 Cravotto G. Cintas P. Chem. Eur. J. 2007, 13: 1902

Crossref Search in Google Scholar
7 The use of 1-(3-chlorophenyl)piperazine refers to the work of: Narayan N. Muldoon J. Finn MG. Fikin VV. Kolb HC. Sharpless KB. Angew. Chem. Int. Ed. 2005, 44: 3275

Crossref PubMed Search in Google Scholar
8 Cravotto G. Omiccioli G. Stevanato L. Ultrason. Sonochem. 2005, 12: 213

Crossref Search in Google Scholar
9 Cravotto G. Boffa L. Bia M. Bonrath W. Curini M. Heropoulos GA. Synlett 2006, 2605

Thieme Connect
10 Cravotto G, Buffa C, and Omiccioli G. inventors; TO patent application A000766.
11 HSAB theory: Huyskens P. Sobczyk L. Majerz I. J. Mol. Struct. 2002, 615: 61

Crossref Search in Google Scholar
12 Azizi N. Saidi MR. Org. Lett. 2005, 7: 3649

Crossref PubMed Search in Google Scholar
13a Newhall WF. J. Org. Chem. 1964, 29: 185

Crossref Search in Google Scholar
13b Steiner D. Ivison L. Goralski CT. Appell RB. Gojkovic JR. Singaram B. Tetrahedron: Asymmetry 2002, 13: 2359

Crossref Search in Google Scholar
13c Davis CE. Bailey JL. Lockner JW. Coates RM. J. Org. Chem. 2003, 68: 75

Crossref Search in Google Scholar

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General Procedure
In a 50 mL two-necked round-bottomed flask (equipped with an optical-fiber thermometer for reactions under MW or combined US/MW) the epoxide (2.5 mmol), the amine (or NaN₃, 2.5 mmol), and H₂O (15 mL) were mixed and subjected to procedures 1-4.

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2-[4-(3-Chlorophenyl)piperazin-1-yl]-2-phenylethanol (1Aα): pale yellow oil; R _f = 0.56 (CHCl₃-MeOH, 19:1). IR (film): 3584, 1595, 1452, 1238, 1028, 954, 765 cm^-1. ¹H NMR (300 MHz, CDCl₃): δ = 7.37-7.22 (m, 5 H, H-2′, -3′, -4′, -5′, -6′), 7.14 (t, J = 8.1 Hz, 1 H, H-5′′′), 6.83-6.72 (m, 3 H, H-2′′′, -4′′′, -6′′′), 4.03 (m, 1 H, H-2), 3.74 (m, 2 H, H-2, -3), 3.20 (m, 4 H, H-3′′a,b, H-5′′a,b), 2.74-2.54 (m, 4 H, H-2′′a,b, H-6′′a,b). MS (CI, isobutane): m/z = 317 [MH]⁺.

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2-[4-(3-Chlorophenyl)piperazin-1-yl]-1-phenylethanol (1Aβ): pale yellow oil; R _f = 0.43 (CHCl₃-MeOH, 19:1). IR (film): 3400, 1595, 1566, 1481, 1244, 1057, 947, 777 cm^-1. ¹H NMR (300 MHz, CDCl₃): δ = 7.46-7.38 (m, 5 H, H-2′, -3′, -4′, -5′, -6′), 7.22 (t, J = 8.1 Hz, 1 H, H-5′′′), 6.94-6.83 (m, 2 H, H-2′′′, -4′′′, -6′′′), 4.86 (m, 1 H, H-1), 3.31 (m, 4 H, H-3′′a,b, H-5′′a,b), 2.95-2.92 (m, 2 H, H-2′′a,b), 2.70-2.56 (m, 4 H, H-2, -3, H-6′′a,b). MS (CI, isobutane): m/z = 317 [MH]⁺.

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2-{3-[4-(3-Chlorophenyl)piperazin-1-yl]-2-hydroxypropyl} isoindoline-1,3-dione (2Aβ): pale yellow oil; R _f = 0.39 (CHCl₃-MeOH, 19:1). IR (film): 3327, 1626, 1576, 1437, 1244, 893 cm^-1. ¹H NMR (300 MHz, CDCl₃): δ = 7.87-7.81 (m, 4 H, H-3, -4, -5, -6,), 7.17 (m, 1 H, H-5′′′), 6.80-6.65 (m, 3 H, H-2′′′, -4′′′, -6′′′), 4.21 (m, 1 H, H-2′), 3.50 (m, 2 H, H-1′a,b), 2.57 (m, 2 H, H-3′a,b), 2.90-2.40 (m, 8 H, H-2′′a,b, H-3′′a,b, H-5′′a,b, H-6′′a,b). MS (CI, isobutane): m/z = 400 [MH]⁺.

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1-[4-(3-Chlorophenyl)piperazin-1-yl]octan-2-ol (3Aβ): pale yellow oil; R _f = 0.40 (hexane-EtOAc, 7:3). IR (film): 3460, 1595, 1487, 1234, 1153, 987, 837, 769 cm^-1. ¹H NMR (300 MHz, CDCl₃): δ = 7.10 (t, J = 8.1 Hz, 1 H, H-2′′), 6.85-6.50 (m, 3 H, H-4′′, -5′′, -6′′), 3.70 (m, 1 H, H-2), 3.10 (m, 4 H, H-3′a,b, H-5′a,b), 2.75 (m, 2 H, H-2′a,b), 2.50 (m, 2 H, H-6′a,b), 2.30 (m, 2 H, H-1a,b), 1.50-1.00 (m, 10 H, H-3a,b, H-4a,b, H-5a,b, H-6a,b, H-7a,b), 0.95 (br s, 3 H, CH₃). MS (CI, isobutane): m/z = 325 [MH]⁺.

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trans-2-[4-(3-Chlorophenyl)piperazin-1-yl]cyclohexanol (4A): pale yellow oil; R _f = 0.13 (PE-EtOAc, 8:2). IR (film): 3462, 1597, 1495, 1263, 1105, 1014, 954, 771, 681 cm^-1. ¹H NMR (300 MHz, CDCl₃): δ = 7.02-6.77 (m, 4 H, H-2′′, -4′′, -5′′, -6′′), 4.16 (m, 1 H, H-1), 3.43 (m, 1 H, H-2), 3.23-3.19 (m, 4 H, H-3′a,b, H-5′a,b), 2.88 (m, 2 H, H-2′a,b), 2.58 (m, 2 H, H-5′a,b), 2.40-1.15 (m, 8 H, H-3,a,b, H-4a,b, H-5a,b, H-6a,b). MS (CI, isobutane): m/z = 295 [MH]⁺.

20

(1R,2R)-2-[4-(3-Chlorophenyl)piperazin-1-yl]-1-methyl-4-(prop-1-en-2-yl)cyclohexanol (5Aβ): pale yellow oil; R _f = 0.62 (hexane-EtOAc, 7:3). IR (film): 3462, 2361, 1595, 1450, 1238, 1126, 987, 767 cm^-1. ¹H NMR (300 MHz, CDCl₃): δ = 7.17 (t, J = 8.1 Hz, 1 H, H-2′′′), 6.87 (m, 3 H, H-4, -5, -6), 4.96 (m, 1 H, H-9a), 4.87 (m, 1 H, H-9b), 3.47 (m, 1 H, H-2), 3.22 (m, 4 H, H-3′′a,b, H-5′′a,b), 2.90 (m, 2 H, H-2′′a,b), 2.68 (m, 2 H, H6′′a,b), 2.5 (br s, 1 H, OH). MS (CI, isobutane): m/z = 349 [MH]⁺.

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(1R,2R,4R)-2-Azido-1-methyl-4-(prop-1-en-2-yl)cyclo-hexanol (5Bβ): colorless oil; R _f = 0.24 (CHCl₃-MeOH, 19:1). IR (film): 3450, 2094, 1645, 1454, 1261, 1032, 891 cm^-1. ¹H NMR (300 MHz, CDCl₃): δ = 4.8 (m, 2 H, H-9a,b), 3.55 (br s, 1 H, H-2), 2.20 (m, 1 H, H-4), 2.00 (m, 1 H, H-3a), 1.85 (m, 1 H, H-3b), 1.73 (m, 3 H, H-10, CH₃), 1.45 (br s, 1 H, OH), 1.40 (m, 3 H, H-7, CH₃). MS (CI, isobutane): m/z = 196 [MH]⁺.