Synthesis of Highly Functionalized 1,3-Oxathioles via an Unusual [4+1] Annulation of α,α'-Dioxothione with 1,2-Diaza-1,3-dienes

Orazio A. Attanasi; Gianfranco Favi; Fabio Mantellini; Stefano Menichetti; Giada Moscatelli; Caterina Viglianisi

doi:10.1055/s-0032-1317621

Synlett, Inhaltsverzeichnis

Synlett 2012; 23(20): 2947-2950
DOI: 10.1055/s-0032-1317621

letter

Synthesis of Highly Functionalized 1,3-Oxathioles via an Unusual [4+1] Annulation of α,α'-Dioxothione with 1,2-Diaza-1,3-dienes

Autoren

Orazio A. Attanasi*

^aDipartimento di Scienze della Terra, della Vita e dell’Ambiente (DiSTeVA), Sezione di Chimica Organica e delle Sostanze Organiche Naturali (SCOSON), Università degli Studi di Urbino ‘Carlo Bo’, Via I Maggetti 24, 61029 Urbino (PU), Italy Fax: +39(722)3033441 eMail: orazio.attanasi@uniurb.it
Gianfranco Favi

^aDipartimento di Scienze della Terra, della Vita e dell’Ambiente (DiSTeVA), Sezione di Chimica Organica e delle Sostanze Organiche Naturali (SCOSON), Università degli Studi di Urbino ‘Carlo Bo’, Via I Maggetti 24, 61029 Urbino (PU), Italy Fax: +39(722)3033441 eMail: orazio.attanasi@uniurb.it
Fabio Mantellini

^aDipartimento di Scienze della Terra, della Vita e dell’Ambiente (DiSTeVA), Sezione di Chimica Organica e delle Sostanze Organiche Naturali (SCOSON), Università degli Studi di Urbino ‘Carlo Bo’, Via I Maggetti 24, 61029 Urbino (PU), Italy Fax: +39(722)3033441 eMail: orazio.attanasi@uniurb.it
Stefano Menichetti*

^bDipartimento di Chimica ‘Ugo Schiff’ Polo Scientifico e Tecnologico, Università di Firenze, Via della Lastruccia 3-13, 50019 Sesto Fiorentino, Italy
Giada Moscatelli

^aDipartimento di Scienze della Terra, della Vita e dell’Ambiente (DiSTeVA), Sezione di Chimica Organica e delle Sostanze Organiche Naturali (SCOSON), Università degli Studi di Urbino ‘Carlo Bo’, Via I Maggetti 24, 61029 Urbino (PU), Italy Fax: +39(722)3033441 eMail: orazio.attanasi@uniurb.it
Caterina Viglianisi

^bDipartimento di Chimica ‘Ugo Schiff’ Polo Scientifico e Tecnologico, Università di Firenze, Via della Lastruccia 3-13, 50019 Sesto Fiorentino, Italy

Abstract

Alle Artikel dieser Rubrik

Abstract

The present method provides highly functionalized 1,3-oxathioles through an unusual base-promoted [4+1] annulation between α,α'-dioxothione, generated in situ from a phthalimide precursor, and 1,2-diaza-1,3-dienes. An intriguing scaffold comprised of spiro-fused oxathiole and pyrazolone components was also obtained in moderate yield.

Key words

oxathioles - Michael addition - [4+1] annulation - spiro compounds

Volltext

Referenzen

References and Notes
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17 Typical Procedure: To a solution of DD 3a (0.171 g, 1.0 mmol) in CH₂Cl₂ (4 mL) were added DTPht 1a (0.614 g, 2.0 mmol) and anhydrous pyridine (0.158 g, 2 mmol) at 25 °C. The solution was stirred for 2 h at room temperature (reaction monitored by TLC analysis). The solvent was removed in vacuo and the residue was purified by column chromatography (silica gel; cyclohexane–EtOAc, 20:80) to give the corresponding oxathiole derivative 4a as a pale-yellow waxy solid (0.191 g, 58%). 4-Ethyl 2-Methyl 2-[1-(2-Carbamoylhydrazono)ethyl]-5-methyl-1,3-oxathiole-2,4-dicarboxylate (4a): ¹H NMR (400 MHz, CDCl₃): δ = 1.29 (t, J = 7.2 Hz, 3 H), 2.02 (s, 3 H), 2.32 (s, 3 H), 3.84 (s, 3 H), 4.21 (q, J = 7.2 Hz, 2 H), 5.00 and 5.98 (br s, 2 H), 8.78 (s, 1 H). ¹³C NMR (100 MHz, CDCl₃): δ = 11.8 (q), 14.2 (q), 14.4 (q), 53.5 (q), 61.2 (t), 96.7 (s), 101.8 (s), 142.2 (s), 157.3 (s), 158.8 (s), 162.4 (s), 168.5 (s). IR (Nujol): 3466, 1746, 1716, 1648, 1592, 1290, 1253, 1087, 1062 cm^–1. MS: m/z (%) = 331 (10), 314 (48), 288 (18), 271 (100), 243 (38), 229 (30), 199 (45), 157 (50). Anal. Calcd for C₁₂H₁₇N₃O₆S (331.34): C, 43.50; H, 5.17; N, 12.68. Found: C, 43.64; H, 5.08; N, 12.59.

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20 To a solution of oxathiole 4e (0.194 g, 0.5 mmol) in CH₂Cl₂ (4 mL) was added TFA (0.057 g, 0.5 mmol) at 25 °C. The solution was stirred for 2 h at r.t., the solvent was removed in vacuo and the residue was purified by column chromatography (silica gel; cyclohexane–EtOAc, 80:20) to give 5 as a pale-yellow waxy solid (0.048 g, 38%). Ethyl 2,6-Dimethyl-9-oxo-1-oxa-4-thia-7,8-diazaspiro-[4.4]nona-2,6-diene-3-carboxylate (5): ¹H NMR (400 MHz, CDCl₃): δ = 1.29 (t, J = 7.2 Hz, 3 H), 2.20 (s, 3 H), 2.31 (s, 3 H), 4.22 and 4.23 (q, J = 7.2 Hz, 2 H), 8.57 (s, 1 H). ¹³C NMR (100 MHz, CDCl₃): δ = 12.7 (q), 14.2 (q), 14.3 (q), 61.4 (t), 87.8 (s), 101.7 (s), 156.9 (s), 159.0 (s), 161.8 (s), 171.7 (s). IR (Nujol): 3349, 3200, 1736, 1712, 1641, 1284, 1087 cm^–1. MS: m/z (%) = 256 (35) [M]⁺, 213 (100), 185 (66), 141 (36). Anal. Calcd for C₁₀H₁₂N₂O₄S (256.28): C, 46.87; H, 4.72; N, 10.93. Found: C, 46.74; H, 4.77; N, 11.01.
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