One-Pot Stereoselective Synthesis of Pyrano[3,2-c]benzothiopyrans: A New Generation and [4+2] Cycloaddition of ortho-Thioquinonemethides

Seiichi Inoue; Ping Wang; Mami Nagao; Yujiro Hoshino; Kiyoshi Honda

doi:10.1055/s-2005-862379

LETTER

One-Pot Stereoselective Synthesis of Pyrano[3,2-c]benzothiopyrans: A New Generation and [4+2] Cycloaddition of ortho-Thioquinonemethides

Seiichi Inoue*^a, Ping Wang^a, Mami Nagao^a, Yujiro Hoshino^a, Kiyoshi Honda^b
^a Department of Environment and Natural Sciences, Graduate School of Environment and Information Sciences, Yokohama National University, 79-7, Tokiwadai, Hodogaya, Yokohama 240-8501, Japan
Fax: +81(45)3351536; e-Mail: s-inoue@ynu.ac.jp;
^b Department of Chemistry and Biotechnology, Graduate School of Engineering, Yokohama National University, 79-7, Tokiwadai, Hodogaya, Yokohama 240-8501, Japan

Abstract

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Abstract

Pyrano[3,2-c]benzothiopyrans are synthesized from thiosalicylaldehyde derivatives and unsaturated alcohols in the presence of trimethyl orthoformate and a catalytic amount of p-toluenesulfonic acid with complete trans-stereoselectivity via intramolecular [4+2] cycloaddition of ortho-thioquinonemethides. A more efficient generation and cycloaddition of ortho-thioquinonemethides with Lewis acid is also described.

Key words

stereoselective synthesis - [4+2] cycloaddition - Lewis acid - sulfur - heterocycles

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References

<A NAME="RU32004ST-1A">1a</A> Ellis GP. Lockhart IM. In Chromans and Tocopherols Vol. 36: John Wiley and Sons; New York: 1981. p.1-58

<A NAME="RU32004ST-1B">1b</A> Cinganek E. In Organic Reactions Vol. 32: Dauben WG. John Wiley and Sons; New York: 1984. p.79

<A NAME="RU32004ST-1C">1c</A> Ingal AH. In Comprehensive Heterocyclic Chemistry Vol. 3: Boulton AS. Mckillop A. Pergamon Press; Oxford: 1984. p.773

<A NAME="RU32004ST-1D">1d</A> Talley JJ. J. Org. Chem. 1985, 50: 1695

<A NAME="RU32004ST-1E">1e</A> Hepworth JD. Heron BM. In Progress in Heterocyclic Chemistry Vol. 15: Gribble GW. Joule JA. Pergamon Press; Amsterdam: 2003. p.360-384

<A NAME="RU32004ST-2A">2a</A> Boger DL. Weinreb SM. In Hetero Diels-Alder Methodology in Organic Synthesis Academic Press; New York: 1987. p.193-197

<A NAME="RU32004ST-2B">2b</A> Boger DL. Weinreb SM. In Hetero Diels-Alder Methodology in Organic Synthesis Academic Press; New York: 1987. p.225

<A NAME="RU32004ST-2C">2c</A> Inamoto N. Heteroat. Chem. 2001, 12: 183

<A NAME="RU32004ST-2D">2d</A> Okazaki R. Ishii F. Inamoto N. Bull. Chem. Soc. Jpn. 1978, 51: 309

<A NAME="RU32004ST-3A">3a</A> Kaye PT. Nocanda XW. Synthesis 2001, 2389

<A NAME="RU32004ST-3B">3b</A> Katritzky AR. Button MAC. J. Org. Chem. 2001, 66: 5595

<A NAME="RU32004ST-3C">3c</A> Kumar P. Bodas MS. Tetrahedron 2001, 57: 9755

<A NAME="RU32004ST-3D">3d</A> Ram VJ. Agarwal N. Saxena AS. Farhanullah S. Sharon A. Maulik PR. J. Chem. Soc., Perkin Trans. 1 2002, 1426

<A NAME="RU32004ST-4">4</A> Saito T. Horikoshi T. Otani T. Matsuda Y. Karakasa T. Tetrahedron Lett. 2003, 44: 6513

<A NAME="RU32004ST-5">5</A> Wermuth CG. The Practice of Medicinal Chemistry Academic Press; London: 1996. p.258

<A NAME="RU32004ST-6A">6a</A> Inoue S. Asami M. Honda K. Miyazaki H. Chem. Lett. 1996, 889

<A NAME="RU32004ST-6B">6b</A> Miyazaki H. Honda K. Asami M. Inoue S. J. Org. Chem. 1999, 64: 9507

<A NAME="RU32004ST-6C">6c</A> Miyazaki H. Honda Y. Honda K. Inoue S. Tetrahedron Lett. 2000, 41: 2643

<A NAME="RU32004ST-7">7</A> For a review of ortho-thioquinonemethide see: Inoue S. Honda K. Kagaku Kogyo 2004, 55: 212 ; Journal written in Japanese

<A NAME="RU32004ST-8A">8a</A> Arnoldi A. Carughi M. Synthesis 1988, 155

<A NAME="RU32004ST-8B">8b</A> Kasmai HS. Mischke SG. Synthesis 1989, 763

<A NAME="RU32004ST-8C">8c</A> Toste FD. Lough AJ. Still IWJ. Tetrahedron Lett. 1995, 36: 6619

<A NAME="RU32004ST-8D">8d</A> Gallagher T. Pardoe DA. Porter RA. Tetrahedron Lett. 2000, 41: 5415

Compound 5a: ¹H NMR (400 MHz, CDCl₃): δ = 1.21 (d, J = 6.1 Hz, 3 H), 1.45 (m, 1 H), 1.50 (s, 3 H), 1.71-1.80 (m, 2 H), 1.92 (m, 1 H), 2.47 (ddd, J = 2.9, 10.0, 11.5 Hz, 1 H), 3.42 (s, 3 H), 3.67 (dqd, J = 2.0, 6.1, 11.1 Hz, 1 H), 4.60 (m, 2 H), 4.85 (d, J = 11.2 Hz, 1 H), 4.93 (d, J = 11.2 Hz, 1 H), 4.95 (d, J = 10.0 Hz, 1 H), 7.21 (ddd, J = 1.7, 7.3, 7.6 Hz, 1 H), 7.23 (ddd, J = 1.5, 7.3, 7.6 Hz, 1 H), 7.43 (dd, J = 1.7, 7.6 Hz, 1 H), 7.56 (dd, J = 1.5, 7.6 Hz, 1 H). ¹³C NMR (100 MHz, CDCl₃): δ = 21.4, 22.2, 30.7, 33.7, 48.5, 56.1, 74.4, 78.6, 79.5, 112.3, 127.2, 127.6, 128.0, 131.6, 135.5, 141.4, 145.8.

Compound 6 was purified by silica gel column chromatography, and was characterized by NMR.

<A NAME="RU32004ST-11A">11a</A> Ishihara K. In Lewis Acid Reagents Yamamoto H. Oxford University Press; New York: 1999. p.31-64

<A NAME="RU32004ST-11B">11b</A> Lin GQ. Li YM. Chan ASC. In Principles and Applications of Asymmetric Synthesis Wiley-Interscience; Great Britain: 2001. p.267-330

<A NAME="RU32004ST-11C">11c</A> Hayashi Y. In Cycloaddition Reactions in Organic Synthesis Kobayashi S. Jørgensen KA. Wiley-VCH; Weinheim (Germany): 2002. p.5-56

<A NAME="RU32004ST-12A">12a</A> Okauchi T. Tanaka T. Minami T. J. Org. Chem. 2001, 66: 3924

<A NAME="RU32004ST-12B">12b</A> Yadav JS. Reddy BVS. Aruna M. Thomas M. Synthesis 2002, 217