Efficient Synthesis of Novel 3-Substituted Thiopyran-4-ones

M. Saeed Abaee; Mohammad M. Mojtahedi; M. Mehdi Zahedi; Roholah Sharifi; Hamidreza Khavasi

doi:10.1055/s-2007-990806

PAPER

Efficient Synthesis of Novel 3-Substituted Thiopyran-4-ones

M. Saeed Abaee^a, Mohammad M. Mojtahedi*^a, M. Mehdi Zahedi^a, Roholah Sharifi^a, Hamidreza Khavasi^b
^a Organic Chemistry Department, Chemistry & Chemical Engineering Research Center of Iran, P. O. Box 14335-186, Tehran, Iran
^b Department of Chemistry, Shahid Beheshti University, Evin, Tehran 1983963113, Iran
Fax: +98(21)44580762; e-Mail: mojtahedi@ccerci.ac.ir;

Abstract

All articles of this category

Abstract

Synthesis of several 3-substituted thiopyran-4-ones is reported for the first time via aldol condensation of various aromatic aldehydes with dihydrothiopyran-4-one derivatives under very mild conditions using magnesium bromide diethyl etherate and triethylamine. The products were characterized based on spectroscopic and X-ray diffraction experiments.

Key words

thiopyrans - aldol condensation - magnesium bromide diethyl etherate - heterocycles

Full Text

References

<A NAME="RT08407SS-1A">1a</A> Rosiak A. Frey W. Christoffers J. Eur. J. Org. Chem. 2006, 4044

<A NAME="RT08407SS-1B">1b</A> Lucassen ACB. Zwanenburg B. Eur. J. Org. Chem. 2004, 74

<A NAME="RT08407SS-1C">1c</A> Poleschner H. Seppelt K. Eur. J. Org. Chem. 2001, 2477

<A NAME="RT08407SS-1D">1d</A> Ward DE. Gai Y. Lai Y. Synlett 1996, 261

<A NAME="RT08407SS-1E">1e</A> Lane S. Quick SJ. Taylor RK. J. Chem. Soc., Perkin Trans. 1 1984, 2549

<A NAME="RT08407SS-2A">2a</A> Ward DE. Gai Y. Can. J. Chem. 1997, 75: 681

<A NAME="RT08407SS-2B">2b</A> Ward DE. Nixey TE. Gai Y. Hrapchak MJ. Abaee MS. Can. J. Chem. 1996, 74: 1418

<A NAME="RT08407SS-2C">2c</A> Ward DE. Nixey TE. Tetrahedron Lett. 1993, 34: 947

<A NAME="RT08407SS-3A">3a</A> Ward DE. Gillis HM. Akinnusi OT. Rasheed MA. Saravanan K. Sasmal PK. Org. Lett. 2005, 7: 2631

<A NAME="RT08407SS-3B">3b</A> Ward DE. Jheengut V. Akinnusim OT. Org. Lett. 2005, 7: 1181

<A NAME="RT08407SS-3C">3c</A> Ward DE. Olukayode TA. Idralyn QA. Vishal J. Jianheng S. Quail W. Tetrahedron: Asymmetry 2004, 15: 2425

<A NAME="RT08407SS-3D">3d</A> Ward DE. Jheengut V. Akinnusim OT. Tetrahedron Lett. 2004, 45: 8347

<A NAME="RT08407SS-3E">3e</A> Ward DE. Sales M. Sasmal PK. J. Org. Chem. 2004, 67: 4808

<A NAME="RT08407SS-3F">3f</A> Ward DE. Sales M. Man C. Jianheng S. Pradip KS. Cheng G. J. Org. Chem. 2002, 67: 1618

<A NAME="RT08407SS-4">4</A> Abaee MS. Mojtahedi MM. Zahedi MM. Synlett 2005, 2317

<A NAME="RT08407SS-5">5</A> This type of aldol condensation followed by hydrogen atom rearrangement has precedence in heterocyclic and for 2,3-dihydropyridin-4(1H)-one systems as previously reported: Kitagawa H. Kumura K. Atsumi K. Chem. Lett. 2006, 712

<A NAME="RT08407SS-6A">6a</A> Ulrich EA. Batson WA. Tius MA. Synthesis 2006, 2139

<A NAME="RT08407SS-6B">6b</A> Grant GTN. West FG. J. Am. Chem. Soc. 2006, 128: 9348

<A NAME="RT08407SS-6C">6c</A> Douelle F. Tal L. Greaney MF. Chem. Commun. 2005, 660

<A NAME="RT08407SS-6D">6d</A> Wang Y. Schill BD. Arif AM. West FG. Org. Lett. 2003, 5: 2747

<A NAME="RT08407SS-7">7</A> Tipparaju SK. Synlett 2004, 912 ; and references cited therein

<A NAME="RT08407SS-8">8</A> Ward DE. Abaee MS. Org. Lett. 2000, 2: 3937

<A NAME="RT08407SS-9">9</A> Abaee MS. Sharifi R. Mojtahedi MM. Org. Lett. 2005, 7: 5893

<A NAME="RT08407SS-10">10</A> Abaee MS. Mojtahedi MM. Zahedi MM. Sharifi R. Heteroat. Chem. 2007, 18: 44

<A NAME="RT08407SS-11">11</A> Mojtahedi MM. Abaee MS. Abbasi H. Can. J. Chem. 2006, 84: 429

<A NAME="RT08407SS-12">12</A> Mojtahedi MM. Abbasi H. Abaee MS. J. Mol. Catal. A: Chem. 2006, 250: 6

<A NAME="RT08407SS-13">13</A> Abaee MS. Mojtahedi MM. Zahedi MM. Khanalizadeh G. ARKIVOC 2006, (xv): 48

<A NAME="RT08407SS-14A">14a</A> Mojtahedi MM. Abaee MS. Bolourtchian M. Abbasi H. Phosphorus, Sulfur and Silicon 2007, 182: 905

<A NAME="RT08407SS-14B">14b</A> Mojtahedi MM. Abaee MS. Hamidi V. Catal. Commun. 2007, 8: 1671

The reaction is limited to aldehydes with no α-hydrogen. Under the conditions, aliphatic aldehydes undergo self condensation and the starting ketone remains intact.

Crystallographic data for 6c have been deposited with the Cambridge Crystallographic Data Center as supplementary publication no. CCDC-627143. Copies of these data can be obtained free of charge on application to CCDC, 12 Union Road, Cambridge CB2 1EZ, UK [Fax: +44(1223)336033; E-mail: deposit@ccdc.cam.ac.uk or via www.ccdc.cam.ac.uk/conts/retrieving.html].

<A NAME="RT08407SS-17">17</A> For previous procedure for the synthesis of 3b, see: Kansal KK. Taylor RK. J. Chem. Soc., Perkin Trans. 1 1984, 703

<A NAME="RT08407SS-18A">18a</A> Ward DE. Rasheed MA. Gillis HM. Beye GE. Jheengut V. Achonduh GT. Synthesis 2007, 1584

<A NAME="RT08407SS-18B">18b</A> Chen CH. Reynolds GA. Van Allen JA. J. Org. Chem. 1977, 42: 2777