Synthesis and Structure of Thia and Selena Heterocycles Containing Cycloamidine Substructures

Abstract

Cyclization of a bis-arylimidoyl chloride with an acylselenourea leads to the construction of a 1,3-selenazolidine with a heteroradialene structure. Another reaction of the bis-arylimidoyl chloride (hydrazinolysis) leads to the formation of Δ²-1,2-diazetines, which we have shown previously to be reactive precursors for ring transformation reactions that yield unusual heterocycles. We now demonstrate that the reaction of these Δ²-1,2-diazetines with various isothio- or isoselenocyanates affords an efficient entry to highly substituted 1,3,4-thia- or -selenadiazines. The structures of these novel derivatives were confirmed by NMR and mass spectroscopy, elemental analysis, and X-ray structural analysis. Detailed multidimensional ⁷⁷Se NMR experiments as well as density functional theory (DFT) calculations show structural specifics of these compounds.

ring expansion - heterocycles - selenium - sulfur - non­covalent chalcogen interactions

References

<A NAME="RZ12507SS-1A">1a</A> Schwarz K. Foltz CM. J. Am. Chem. Soc.  1957,  79:  3292 

<A NAME="RZ12507SS-1B">1b</A> Ursini F. Bindoli A. Chem. Phys. Lipids  1987,  44:  255 

<A NAME="RZ12507SS-1C">1c</A> Stadtman T. Annu. Rev. Biochem.  1990,  59:  111 

<A NAME="RZ12507SS-1D">1d</A> Forchhammer K. Böck A. Naturwissenschaften  1991,  78:  497 

<A NAME="RZ12507SS-1E">1e</A> Stadtman T. J. Biol. Chem.  1991,  266:  16257 

<A NAME="RZ12507SS-1F">1f</A> Stadtman T. Annu. Rev. Biochem.  1996,  65:  83 

<A NAME="RZ12507SS-2A">2a</A> Kirsi JJ. McKernan PA. Burns NJ. North JA. Murray BK. Robins RK. Antimicrob. Agents Chemother.  1984,  26:  466 

<A NAME="RZ12507SS-2B">2b</A> Robins RK. Revankar GR. McKernan PA. Murray BK. Kirsi JJ. North JA. Adv. Enzyme Regul.  1985,  24:  29 

<A NAME="RZ12507SS-2C">2c</A> Gebeyehu G. Marquez VE. Van Cott A. Cooney DA. Kelley JA. Jayaram HN. Ahluwalia GS. Dion RL. Wilson YA. Johns DG. J. Med. Chem.  1985,  28:  99 

<A NAME="RZ12507SS-2D">2d</A> Natsumeda Y. Yamada Y. Yamaji Y. Weber G. Biochem. Biophys. Res. Commun.  1988,  153:  321 

<A NAME="RZ12507SS-2E">2e</A> Franchetti P. Cappellacci L. Abu Sheikha G. Jayaram HN. Gurudutt VV. Sint T. Schneider BP. Jones WD. Goldstein BM. Perra G. De Montis A. Loi AG. La Colla P. Grifantini M. J. Med. Chem.  1997,  40:  1731 

<A NAME="RZ12507SS-2F">2f</A> Parker WB. Virus Res.  2005,  107:  165 

<A NAME="RZ12507SS-2G">2g</A> Sarma BK. Mugesh G. J. Am. Chem. Soc.  2005,  127:  15207 

<A NAME="RZ12507SS-3A">3a</A> Shinkai I. Larsen RD. In Comprehensive Heterocyclic Chemistry II   Vol. 3:  Pergamon; New York: 1996.  p.493-510  

<A NAME="RZ12507SS-3B">3b</A> Boulton AJ. Smalley RK. Sainsbury M. In Comprehensive Heterocyclic Chemistry II   Vol. 6:  Pergamon; New York: 1996.  737-783. p.987-1018  

<A NAME="RZ12507SS-3C">3c</A> Mochowski J. Kloc K. Lisiak R. Potaczek P. Wójtowicz H. Arkivoc  2007,  (vi):  14 

<A NAME="RZ12507SS-3D">3d</A> Garud DR. Koketsu M. Ishihara H. Molecules  2007,  12:  504 

<A NAME="RZ12507SS-4A">4a</A> Beckert R. Mayer R. J. Prakt. Chem.  1982,  324:  227 

<A NAME="RZ12507SS-4B">4b</A> Beckert R. Gruner M. Seidel I. Kuban R.-J. Monatsh. Chem.  1989,  120:  1125 

<A NAME="RZ12507SS-4C">4c</A> Beckert R. Gruner M. J. Prakt. Chem.  1990,  332:  65 

<A NAME="RZ12507SS-4D">4d</A> Brandenburg J. Käpplinger C. Beckert R. Synthesis  1996,  1302 

<A NAME="RZ12507SS-4E">4e</A> Brandenburg J. Beckert R. Fehling P. Döring M. Görls H. J. Prakt. Chem./Chem.-Ztg.  1996,  338:  430 

<A NAME="RZ12507SS-4F">4f</A> Beckert R. Gruner M. Z. Naturforsch., B: Chem. Sci.  1997,  52:  1245 

<A NAME="RZ12507SS-4G">4g</A> Billert T. Beckert R. Fehling P. Döring M. Görls H. Tetrahedron  1997,  53:  5455 

<A NAME="RZ12507SS-4H">4h</A> Käpplinger C. Beckert R. Imhof W. J. Prakt. Chem./Chem.-Ztg.  1998,  340:  323 

<A NAME="RZ12507SS-4I">4i</A> Welzel T. Beckert R. Fischer R. Rau S. Walther D. Görls H. Tetrahedron  2006,  62:  731 

<A NAME="RZ12507SS-5">5</A> Beckert R. Gruner M. J. Prakt. Chem./Chem.-Ztg.  1992,  334:  611 

<A NAME="RZ12507SS-6A">6a</A> Bulka E. Ahlers KD. Z. Chem.  1963,  3:  348 

<A NAME="RZ12507SS-6B">6b</A> Rossberg H. Pfeiffer WD. Bulka E. Wiss. Z. Ernst-Moritz-Arndt-Univ. Greifsw., Math.-Naturwiss. Reihe  1985,  34:  75 

<A NAME="RZ12507SS-6C">6c</A> Pfeiffer WD. Bulka E. Miethchen R. Z. Chem.  1987,  27:  296 

<A NAME="RZ12507SS-6D">6d</A> Pfeiffer WD. Bulka E. Chem.-Ztg.  1991,  115:  361 

<A NAME="RZ12507SS-6E">6e</A> Pfeiffer WD. Rossberg H. Pharmazie  1993,  48:  732 

<A NAME="RZ12507SS-6F">6f</A> Jira T. Pfeiffer WD. Lachmann K. Epperlein U. Pharmazie  1994,  49:  401 

<A NAME="RZ12507SS-6G">6g</A> Jira T. Stelzer A. Pfeiffer WD. Schopplich Ch. Siegert S. Kindermann M. Pharmazie  1997,  52:  831 

<A NAME="RZ12507SS-6H">6h</A> Koketsu M. Nada F. Ishihara H. Synthesis  2002,  195 

<A NAME="RZ12507SS-6I">6i</A> Geisler K. Pfeiffer WD. Künzler A. Below H . Bulka E . Langer P . Synthesis  2004,  875 

<A NAME="RZ12507SS-6J">6j</A> Geisler K. Künzler A. Below H. Bulka E. Pfeiffer W D. Langer P . Synthesis  2004,  97 

<A NAME="RZ12507SS-6K">6k</A> Sommen GL. Linden A. Heimgartner H. Helv. Chim. Acta  2006,  89:  1322 

<A NAME="RZ12507SS-6L">6l</A> Koketsu M. Kogami M. Ando H. Ishihara H. Synthesis  2006,  31 

<A NAME="RZ12507SS-7">7</A> Pufky D. Beckert R. Döring M. Walter O. Heterocycles  2002,  57:  1257 

<A NAME="RZ12507SS-8A">8a</A> Fleischhauer J. Beckert R. Günther W. Görls H. Synthesis  2006,  2885 

<A NAME="RZ12507SS-8B">8b</A> Fleischhauer J. Beckert R. Weston J. Schmidt M. Flammersheim H.-J. Görls H. Synthesis  2006,  514 

<A NAME="RZ12507SS-9">9</A> Beckert R. Fleischhauer J. Darsen A. Weston J. Schenk S. Batista A. Anders E. Görls H. Döring M. Pufky D. Walter O. Heterocycles  2005,  65:  1311 

<A NAME="RZ12507SS-10A">10a</A> Franklin WJ. Werner RL. Tetrahedron Lett.  1965,  34:  3003 

<A NAME="RZ12507SS-10B">10b</A> Barton DHR. Parekh SI. Tajbakhsh M. Theodorakis EA. Tse C.-L. Tetrahedron  1994,  50:  639 

<A NAME="RZ12507SS-10C">10c</A> Atanassov PK. Linden A. Heimgartner H. Helv. Chim. Acta  2004,  87:  1873 

<A NAME="RZ12507SS-11">11</A> Koketsu M. Yamamura Y. Ishihara H. Synthesis  2006,  2738 

<A NAME="RZ12507SS-12A">12a</A> Beer RJS. McMonagle D. Siddiqui MSS. Hordvik A. Jynge K. Tetrahedron  1979,  35:  1199 

<A NAME="RZ12507SS-12B">12b</A> Fabius B. Cohen-Addad C. Larsen FK. Lehmann MS. Becker P. J. Am. Chem. Soc.  1989,  111:  5728 

<A NAME="RZ12507SS-13">13</A> Bleiholder C. Gleiter R. Werz DB. Köppel H. Inorg. Chem.  2007,  46:  2249 

<A NAME="RZ12507SS-14">14</A> Pfeiffer WD. Buhrow J. Bulka E. Wiss. Z. Ernst-Moritz-Arndt-Univ. Greifsw., Math.-Naturwiss. Reihe  1988,  37:  38 

<A NAME="RZ12507SS-15">15</A> Schröder J. Henke A. Wenzel H. Brandstetter H. Stammler HG. Stammler A. Pfeiffer WD. Tschesche H. J. Med. Chem.  2001,  44:  3231 

<A NAME="RZ12507SS-16">16</A>

Orca - an ab initio, DFT, and semiempirical scf-mo package; see: http://www.thch.uni-bonn.de/tc/orca.

<A NAME="RZ12507SS-17">17</A>

Weinhold, F. NBO, version 5; see:
http://www.chem.wisc.edu/˜nbo5/.

<A NAME="RZ12507SS-18">18</A> Tao J. Perdew JP. Staroverov VN. Scuseria GE. Phys. Rev. Lett.  2003,  91:  146401 

<A NAME="RZ12507SS-19">19</A> Weigend F. Ahlrichs R. Phys. Chem. Chem. Phys.  2005,  7:  3297 

<A NAME="RZ12507SS-20A">20a</A> Eichkorn K. Treutler O. Öhm H. Häser M. Ahlrichs R. Chem. Phys. Lett.  1995,  240:  283 

<A NAME="RZ12507SS-20B">20b</A> Eichkorn K. Weigend F. Treutler O. Ahlrichs R. Theor. Chem. Acc.  1997,  97:  119 

<A NAME="RZ12507SS-20C">20c</A> Neese F. J. Comput. Chem.  2003,  24:  1740 

<A NAME="RZ12507SS-21">21</A> Frisch MJ. Trucks GW. Schlegel HB. Scuseria GE. Robb MA. Cheeseman JR. Montgomery JA. Vreven T. Kudin KN. Burant JC. Millam JM. Iyengar SS. Tomasi J. Barone V. Mennucci B. Cossi M. Scalmani G. Rega N. Petersson GA. Nakatsuji H. Hada M. Ehara M. Toyota K. Fukuda R. Hasegawa J. Ishida M. Nakajima T. Honda Y. Kitao O. Nakai H. Klene M. Li X. Knox JE. Hratchian HP. Cross JB. Bakken V. Adamo C. Jaramillo J. Gomperts R. Stratmann RE. Yazyev O. Austin AJ. Cammi R. Pomelli C. Ochterski JW. Ayala PY. Morokuma K. Voth GA. Salvador P. Dannenberg JJ. Zakrzewski VG. Dapprich S. Daniels AD. Strain MC. Farkas O. Malick DK. Rabuck AD. Raghavachari K. Foresman JB. Ortiz JV. Cui Q. Baboul AG. Clifford S. Cioslowski J. Stefanov BB. Liu G. Liashenko A. Piskorz P. Komaromi I. Martin RL. Fox DJ. Keith T. Al-Laham MA. Peng CY. Nanayakkara A. Challacombe M. Gill PMW. Johnson B. Chen W. Wong MW. Gonzalez C. Pople JA. Gaussian03, revision D.01   Gaussian Inc.; Wallingford CT: 2004.  see: http://www.gaussian.com

<A NAME="RZ12507SS-22A">22a</A> Becke AD. Phys. Rev. A: At., Mol., Opt. Phys.  1988,  38:  3098 

<A NAME="RZ12507SS-22B">22b</A> Becke AD. J. Chem. Phys.  1993,  98:  5648 

<A NAME="RZ12507SS-22C">22c</A> Lee C. Yang W. Parr RG. Phys. Rev. B: Condens. Matter Mater. Phys.  1988,  37:  785 

<A NAME="RZ12507SS-23A">23a</A> Hehre WJ. Ditchfield R. Pople JA. J. Chem. Phys.  1972,  56:  2257 

<A NAME="RZ12507SS-23B">23b</A> Hariharan PC. Pople JA. Theor. Chim. Acta  1973,  28:  213 

<A NAME="RZ12507SS-23C">23c</A> Francl MM. Pietro WJ. Hehre WJ. Binkley JS. Gordon MS. DeFrees DJ. Pople JA. J. Chem. Phys.  1982,  77:  3654 

<A NAME="RZ12507SS-24">24</A>

CCDC-644462 (3), CCDC-644463 (7g), and CCDC-644464 (8j) contain the supplementary crystallographic data for this paper. These data can be obtained free of charge via www.ccdc.cam.ac.uk/conts/retrieving.html (or from the Cambridge Crystallographic Data Centre, 12 Union Road, Cambridge CB2 1EZ, UK; fax: [phone]; email: [e-mail]).

<A NAME="RZ12507SS-25">25</A> COLLECT, Data Collection Software   Nonius B.V.; Delft/The Netherlands: 1998. 

<A NAME="RZ12507SS-26">26</A> Otwinowski Z. Minor W. Processing of X-Ray Diffraction Data Collected in Oscillation Mode, In Methods in Enzymology   Vol. 276 Macromolecular Crystallography:  Carter CW. Sweet RM. Academic Press; New York: 1997.  Part A. p.307-326  

<A NAME="RZ12507SS-27">27</A> Sheldrick GM. Acta Crystallogr., Sect. A  1990,  46:  467 

<A NAME="RZ12507SS-28">28</A> Sheldrick GM. SHELXL-97 (Release 97-2)   University of Göttingen; Germany: 1997. 

<A NAME="RZ12507SS-29">29</A> XP. Version 4.1   Siemens Analytical X-ray Instruments Inc.; Madison/Wisconsin: 1990.