Hydrothiophosphorylation of Vinyl Sulfoxides: First Examples

Nina K. Gusarova; Maria V. Bogdanova; Nina I. Ivanova; Nataliya A. Chernysheva; Boris G. Sukhov; Lidiya M. Sinegovskaya; Olga N. Kazheva; Grigorii G. Alexandrov; Oleg A. D’yachenko; Boris A. Trofimov

doi:10.1055/s-2005-918408

PAPER

Hydrothiophosphorylation of Vinyl Sulfoxides: First Examples

Nina K. Gusarova^a, Maria V. Bogdanova^a, Nina I. Ivanova^a, Nataliya A. Chernysheva^a, Boris G. Sukhov^a, Lidiya M. Sinegovskaya^a, Olga N. Kazheva^b, Grigorii G. Alexandrov^c, Oleg A. D’yachenko^b, Boris A. Trofimov*^a
^a A. E. Favorsky Irkutsk Institute of Chemistry, Siberian Branch of the Russian Academy of Sciences, 1 Favorsky Street, 664033 Irkutsk, Russia
Fax: +7(3952)419346; e-Mail: gusarova@irioch.irk.ru;
^b Institute of Problems of Chemical Physics RAS, 1 Semenov Av., 142432 Chernogolovka, Russia
^c Kurnakov Institute of General and Inorganic Chemistry RAS, 31 Leninskii Av., 119991 Moscow, Russia

Abstract

All articles of this category

Abstract

The first examples of facile hydrothiophosphorylation of organyl vinyl sulfoxides are described. Nucleophilic addition of P,S-ambident secondary phosphine sulfides 1 and 2 to organyl vinyl sulfoxides 3-6 with potassium hydroxide at room temperature proceeds chemo- and regioselectively to give the corresponding bis(2-organylethyl)[2-(organylsulfinyl)ethyl]phosphine sulfides 7a-e in high isolated yields.

Key words

hydrothiophosphorylations - vinyl sulfoxides - secondary phosphine sulfides - nucleophilic additions

Full Text

References

<A NAME="RZ09005SS-1A">1a</A> Faller JW. Wilt JC. Parr J. Org. Lett. 2004, 6: 1301

<A NAME="RZ09005SS-1B">1b</A> Skvortsov NK. Spivak VN. Pashnova LV. Bel’skii VK. Russ. J. Gen. Chem. (Engl. Transl.) 1997, 67: 487

<A NAME="RZ09005SS-1C">1c</A> Kalinin AB. Trofimov AE. Skvortsov NK. Russ. J. Gen. Chem. (Engl. Transl.) 1997, 67: 820

<A NAME="RZ09005SS-1D">1d</A> Braunstein P. Naud F. Angew. Chem. Int. Ed. 2001, 40: 680

<A NAME="RZ09005SS-1E">1e</A> Cantat T. Mezailles N. Ricard L. Jean Y. Le Floch P. Angew. Chem. Int. Ed. 2004, 43: 6382

<A NAME="RZ09005SS-1F">1f</A> Imamoto T. Oohara N. Takahashi H. Synthesis 2004, 1353

<A NAME="RZ09005SS-1G">1g</A> Subasi E. Senturk OS. Ugur F. Z. Naturforsch., B: Chem. Sci 2004, 59: 836

<A NAME="RZ09005SS-2A">2a</A> Archer CM. Dilworth JR. Griffiths DV. Hughes JM. Kelly JD. Morton S. In Technetium in Chemistry and Nuclear Medicine Nicolini M. Bandoli G. Mazzi U. SGEditoriali; Padova: 1995. p.173

<A NAME="RZ09005SS-2B">2b</A> Griffiths DV. Groombridge HJ. Mahoney PM. Swetnam SP. Walton G. York DC. Tetrahedron 2005, 61: 4595

<A NAME="RZ09005SS-2C">2c</A> Leung P.-H. Siah S.-Y. White AJP. Williams DJ. J. Chem. Soc., Dalton Trans. 1998, 893

<A NAME="RZ09005SS-2D">2d</A> Hiroi K. Suzuki Y. Kawagishi R. Tetrahedron Lett. 1999, 40: 715

<A NAME="RZ09005SS-2E">2e</A> Quek GH. Leung P.-H. Mok KF. Inorg. Chim. Acta 1995, 239: 185

<A NAME="RZ09005SS-2F">2f</A> Griffiths DV. Caesar JC. Hughes JM. Mahoney PM. Swetnam SP. Walton G. York DC. Phosphorus, Sulfur Silicon Relat. Elem. 1999, 146: 485

<A NAME="RZ09005SS-3A">3a</A> Trofimov BA. Gusarova NK. Malysheva SF. Ivanova NI. Sukhov BG. Belogorlova NA. Kuimov VA. Synthesis 2002, 2207

<A NAME="RZ09005SS-3B">3b</A> Bunlaksananusorn T. Knochel P. Tetrahedron Lett. 2002, 43: 5817

<A NAME="RZ09005SS-3C">3c</A> Trofimov BA. Gusarova NK. Malysheva SF. Ivanova NI. Sukhov BG. Reutskaya AM. Kuimov VA. In Proceedings of the XXth International Symposium on the Organic Chemistry of Sulfur (ISOCS XX) T9: Flagstaff; AZ USA: 2002.

<A NAME="RZ09005SS-4A">4a</A> Malysheva SF. Gusarova NK. Belogorlova NA. Arbuzova SN. Sinegovskaya LM. Zefirov NS. Trofimov BA. Russ. J. Gen. Chem. (Engl. Transl.) 1998, 68: 1638

<A NAME="RZ09005SS-4B">4b</A> Malysheva SF. Gusarova NK. Belogorlova NA. Afonin AV. Arbuzova SN. Trofimov BA. Russ. Chem. Bull. 1997, 46: 1799

<A NAME="RZ09005SS-4C">4c</A> Malysheva SF. Gusarova NK. Belogorlova NA. Trofimov BA. Sulfur Lett. 1998, 21: 263

<A NAME="RZ09005SS-5A">5a</A> Gusarova NK. Malysheva SF. Chernysheva NA. Belogorlova NA. Arbuzova SN. Khil’ko MYa. Trofimov BA. Russ. J. Org. Chem. (Engl. Transl.) 1998, 34: 1056

<A NAME="RZ09005SS-5B">5b</A> Malysheva SF. Ivanova NI. Belogorlova NA. Khil’ko MYa. Larina LI. Gusarova NK. Trofimov BA. Chem. Heterocycl. Compd. (Engl. Transl.) 1998, 1195

<A NAME="RZ09005SS-5C">5c</A> Ivanova NI. Gusarova NK. Malysheva SF. Belogorlova NA. Kozyreva OB. Skotheim T. Trofimov BA. Russ. J. Org. Chem. (Engl. Transl.) 1997, 33: 1515

<A NAME="RZ09005SS-5D">5d</A> Gusarova NK. Ivanova NI. Bogdanova MV. Sinegovskaya LM. Sukhov BG. Kopylova LI. Trofimov BA. Chem. Heterocycl. Compd. (Engl. Transl.) 2004, 1584

<A NAME="RZ09005SS-6">6</A> Chernysheva NA. Gusarova NK. Trofimov BA. Russ. J. Org. Chem. (Engl. Transl.) 2000, 36: 1

<A NAME="RZ09005SS-7">7</A> Peters G. J. Am. Chem. Soc. 1960, 82: 4751

<A NAME="RZ09005SS-8A">8a</A> Trofimov BA. Brandsma L. Arbuzova SN. Malysheva SF. Gusarova NK. Tetrahedron Lett. 1994, 35: 7647

<A NAME="RZ09005SS-8B">8b</A> Trofimov BA. Gusarova NK. Arbuzova SN. Russ. Chem. Rev. (Engl. Transl.) 1999, 68: 215

<A NAME="RZ09005SS-9A">9a</A> Trofimov BA. Shaikhudinova SI. Dmitriev VI. Nepomnyashchikh KV. Kazantseva TI. Gusarova NK. Russ. J. Gen. Chem. (Engl. Transl.) 2000, 70: 40

<A NAME="RZ09005SS-9B">9b</A> Malysheva SF. Arbuzova SN. In Sovremenniy organicheskiy sintez (Modern Organic Synthesis) Rakhmankoulov DL. Chemistry; Moscow: 2003. p.160

<A NAME="RZ09005SS-10">10</A> Well M. Schmutzler R. Phosphorus, Sulfur Silicon Relat. Elem. 1992, 72: 171

<A NAME="RZ09005SS-11">11</A> The positions of resonance in the ¹H, ¹³C and ³¹P NMR spectra (CDCl₃) of compounds 1 and 2 which reflect magnetic interaction of the phosphorus atom (³¹P) with its immediate neighborhood (¹H, ¹³C), as well as doublets in ¹H and ³¹P spectra with the direct coupling constants ¹ J _PH = 442.3 and 447.5 Hz for 1 and 2, respectively, indicate that phosphine sulfides 1 and 2 exist in the thione form. IR spectra of 1 and 2 show absorption bands of stretching vibrations at 567-570 (P=S) and 2330-2363 cm^-1 (P-H), characteristic of secondary phosphine sulfides, see: Maier L. Helv. Chim. Acta 1966, 49: 1249

<A NAME="RZ09005SS-12">12</A> X-ray crystal analysis was performed on an Enraf Nonius CAD4 diffractometer (graphite monochromator ω-scanning Mo Kα radiation). The crystal structure was solved by direct methods using the SHELXS-97 program package and refined anisotropically by the full matrix least square method for all nonhydrogen atoms using the SHELXL-97 program, see: Sheldrick GM. SHELXS-97, SHELXL-97, Programs for Crystal Structure Determination and Refinement Göttingen University; Germany: 1997. the absorption correction was applied. The coordinates of the H atoms were determined by Fourier synthesis and refined isotropically; R factor is 0.047, a = 6.304 (1) Å, b = 9.329 (2) Å, c = 13.220 (3) Å, α = 88.65 (3)°, β = 89.03 (3)°, γ = 77.89 (3)°, triclinic P-1, Z = 2, Dcalcd = 1.20 g·cm^-3; P(1)=S(1) 1.957 (1) Å, P(1)-C(1) 1.811 (2) Å, P(1)-C(9) 1.811 (2) Å, P(1)-H(1) 1.31 (2) Å. CCDC 269206 contains 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 CCDC, 12 Union Road, Cambridge CB2 1EZ, UK; Fax: +44 (1223)336033; E-mail: deposit@ccdc.cam.ac.uk.

<A NAME="RZ09005SS-13A">13a</A> Trofimov BA. Curr. Org. Chem. 2002, 6: 1121

<A NAME="RZ09005SS-13B">13b</A> Trofimov BA. In Modern Problems of Organic Chemistry issue 14: VVM; St.-Petersburg: 2004. p.121