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, Table of Contents

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

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

› Author Affiliations

Abstract

All articles of this category

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

Full Text

References

References and Notes
1 Wilkins DJ In Modern Heterocyclic Chemistry . Alvarez-Builla J, Vaquero JJ, Barluenga J. Wiley-VCH; Weinheim: 2011: 925

2a Nikolaev VA, Ivanov AV, Shakhim AA, Schulze B, Rodina LL. Russ. J. Org. Chem. 2011; 47: 1911
2b Mataka S, Ishii S, Tashiro M. Chem. Lett. 1977; 955

3a Kägi M, Linden A, Mlostón G, Heimgartner H. Helv. Chim. Acta 1998; 81: 285
3b Bak C, Praefcke K. Chem. Z. 1978; 102: 456

4 Bak C, Praefcke K. Chem. Ber. 1979; 112: 2744
5 Batsila C, Kostakis G, Hadjiarapoglou LP. Tetrahedron Lett. 2002; 43: 5997

6a Nakayama J, Sugiura H, Hoshino M, Kobayashi H. Tetrahedron Lett. 1985; 26: 2201
6b Oka K, Dobashi A, Hara S. J. Am. Chem. Soc. 1981; 103: 2757

7 Capozzi G, Nativi C, Menichetti S, Rosi A, Valle G. Tetrahedron 1992; 48: 9023

8a Menichetti S, Nativi C In Targets in Heterocyclic Systems-Chemistry and Properties . Vol. 7. Attanasi OA, Spinelli D. Società Chimica Italiana; Rome: 2003: 108
8b Capozzi G, Falciani C, Menichetti S, Nativi C, Raffaelli B. Chem.–Eur. J. 1999; 1748
8c Capozzi G, Falciani C, Menichetti S, Nativi C. J. Org. Chem. 1997; 62: 2611
8d Capozzi G, Dios A, Franck RW, Geer A, Marzabadi C, Menichetti S, Nativi C, Tamarez M. Angew. Chem. 1996; 35: 777
8e Capozzi G, Franck RW, Mattioli M, Menichetti S, Nativi C, Valle G. J. Org. Chem. 1995; 60: 6416

9 Capozzi G, Fragai M, Menichetti S, Nativi C. Eur. J. Org. Chem. 1999; 3375
10 Capozzi G, Menichetti S, Nativi C. Eur. J. Org. Chem. 2000; 3653
11 For a review on the chemistry of DDs, see: Attanasi OA, De Crescentini L, Favi G, Filippone P, Mantellini F, Perrulli FR, Santeusanio S. Eur. J. Org. Chem. 2009; 3109
12 For a recent example, see: Attanasi OA, Favi G, Filippone P, Mantellini F, Moscatelli G, Perrulli FR. Org. Lett. 2010; 12: 468
13 Chen J.-R, Dong W.-R, Candy M, Pan F.-F, Jörres M, Bolm C. J. Am. Chem. Soc. 2012; 134: 6924

For some recent examples, see:

14a D’Auria M, Racioppi R, Attanasi OA, Mantellini F. Synlett 2010; 1363
14b Pitacco G, Attanasi OA, De Crescentini L, Favi G, Felluga F, Forzato C, Mantellini F, Nitti P, Valentin E, Zangrando E. Tetrahedron: Asymmetry 2010; 21: 617
14c Attanasi OA, Favi G, Filippone P, Perrulli FR, Santeusanio S. Org. Lett. 2009; 11: 309 ; and references therein

For selected examples, see:

15a Attanasi OA, Bartoccini S, Favi G, Filippone P, Perrulli FR, Santeusanio S. J. Org. Chem. 2012; 77: 9338
15b Attanasi OA, Bartoccini S, Favi G, Giorgi G, Perrulli FR, Santeusanio S. J. Org. Chem. 2012; 77: 1161
15c Battistini L, Dell’Amico L, Sartori A, Curti C, Pelosi G, Casiraghi G, Attanasi OA, Favi G, Zanardi F. Adv. Synth. Catal. 2011; 353: 1966
15d Attanasi OA, De Crescentini L, Favi G, Mantellini F, Nicolini S. J. Org. Chem. 2011; 76: 8320
15e Attanasi OA, De Crescentini L, Favi G, Nicolini S, Perrulli FR, Santeusanio S. Org. Lett. 2011; 13: 353
15f Attanasi OA, Favi G, Mantellini F, Moscatelli G, Santeusanio S. J. Org. Chem. 2011; 76: 2860
15g Attanasi OA, Favi G, Filippone P, Perrulli FR, Santeusanio S. Synlett 2010; 1859
15h Attanasi OA, Favi G, Filippone P, Giorgi G, Lillini S, Mantellini F, Perrulli FR. Synlett 2006; 2731

16a Huang N.-Z, Lakshmikantham MV, Cava MP. J. Org. Chem. 1987; 52: 169
16b Kirby GW, Lochead AW. J. Chem. Soc., Chem. Commun. 1983; 1325
16c Harp DN, Back TG. J. Org. Chem. 1976; 41: 2498

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.

18a Bushby RJ, Mann S. J. Chem. Soc., Perkin Trans. 1 1987; 2497
18b Bak C, Praefcke K. Chem. Ber. 1979; 112: 2744

19 Jacobsson U, Kempe T, Norin T. J. Org. Chem. 1974; 39: 2722
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.
21 El-Saraf GA, El-Sayed AM, El-Saghier AM. M. Heteroat. Chem. 2003; 14: 211