Indium(I) Iodide-Promoted Cleavage of Diaryl Diselenides and Disulfides and Subsequent Condensation with Alkyl or Acyl Halides. One-Pot Efficient Synthesis of Diorganyl Selenides, Sulfides, Selenoesters, and Thioesters Brindaban C. Ranu* and Tanmay Mandal Department of Organic Chemistry, Indian Association for the Cultivation of Science, Jadavpur, Calcutta 700 032, India
[email protected] Received April 15, 2004
Abstract: Diphenyl diselenides and disulfides undergo facile cleavages by indium(I) iodide and the corresponding generated selenate and thiolate anions condense in situ with alkyl or acyl halides present in the reaction mixture. Thus, a simple, efficient, and general procedure has been developed for the synthesis of unsymmetrical diorganyl selenides, sulfides (thioethers), selenoesters, and thioesters by this onepot reaction at room temperature.
The importance of indium metal and its salts has been well demonstrated through novel protocols for carboncarbon bond formation, rearrangements, and a variety of useful reactions over the past decade.1 Thus, the search for new indium derivatives for more improvement in organic transformations is of much current interest.2 As a part of our activities in indium-mediated reactions,1e,3 we are also in this race, and recently we reported the use of indium(I) iodide for the cleavage of diphenyl diselenides followed by in situ condensation of selenate anion with alkyl halides to produce diorganyl selenides in a preliminary communication.4 We demonstrate here further extension of this work together with application of this indium reagent for the cleavage of diaryl disulfides and subsequent reaction with alkyl or acyl halides to provide diorganyl sulfides and thioesters (Scheme 1). * Fax: 91-33-24732805. (1) (a) Cintas, P. Synlett 1995, 1087. (b) Li, C.-J. Tetrahedron 1996, 52, 5643. (c) Li, C.-J.; Chan, T. H. Tetrahedron 1999, 55, 11149. (d) Chauhan, K. K.; Frost, C. G. J. Chem. Soc., Perkin Trans. 1 2000, 3015. (e) Ranu, B. C. Eur. J. Org. Chem. 2000, 2347. (f) Babu, G.; Perumal, P. T. Aldrichimica Acta 2000, 33, 16. (g) Podelech, J.; Maier, T. C. Synthesis 2003, 633. (2) (a) Chauhan, K. K.; Frost, C. G.; Love, I.; Waite, D. Synlett 1999, 1743. (b) Ali, T.; Chauhan, K. K.; Frost, C. G. Tetrahedron Lett. 1999, 40, 5621. (c) Abernethy, C. D.; Cole, M. L.; Davies, A. J.; Jones, C. Tetrahedron Lett. 2000, 41, 7567. (d) Cooper, I. R.; Grigg, R.; MacLachlan, W. S.; Sridharan, V.; Thornton-Pett, M. Tetrahedron Lett. 2003, 44, 403. (e) Villalva-Servin, N. P.; Melekov, A.; Fallis, A. G. Synthesis 2003, 790. (3) (a) Ranu, B. C.; Hajra, A.; Jana, U. J. Org. Chem. 2000, 65, 6270. (b) Ranu, B. C.; Hajra, A.; Jana, U. Tetrahedron Lett. 2000, 41, 531. (c) Ranu, B. C.; Samanta, S.; Hajra, A. Synlett 2002, 987. (d) Ranu, B. C.; Das, A.; Samanta, S. Synlett 2002, 727. (e) Ranu, B. C.; Dey, S. S.; Hajra, A. Tetrahedron 2002, 58, 2529. (f) Ranu, B. C.; Hajra, A.; Dey, S. S.; Jana, U. Tetrahedron 2003, 59, 813. (g) Ranu, B. C.; Samanta, S. J. Org. Chem. 2003, 68, 7130. (h) Ranu, B. C.; Das, A.; Hajra, A. Synthesis 2003, 1012. (i) Ranu, B. C.; Samanta, S. Tetrahedron 2003, 59, 7901. (4) Ranu, B. C.; Mandal, T.; Samanta, S. Org. Lett. 2003, 5, 1439.
SCHEME 1.
Synthesis of Selenides and Sulfides
The experimental procedure is very simple. A mixture of alkyl (or acyl) halide and diaryl selenide (or sulfide) in methylene chloride was stirred in the presence of indium(I) iodide at room temperature for a certain period of time (TLC). Usual workup and extraction with ether provided the product. A wide range of structurally diverse alkyl halides underwent reactions with diphenyl diselenides and disulfides by this procedure to produce the corresponding alkyl phenyl selenides and sulfides (thioethers), respectively, in very high yields. The results are presented in Table 1 for selenides and in Table 2 for sulfides. As evident from Tables 1 and 2, primary, secondary, tertiary, benzylic, and allylic chlorides, bromides, and iodides readily participate in this reaction to form the corresponding products. The reaction with relatively sterically congested-bridged halide also proceeds without any difficulty (entry 23 in Table 1). However, the reaction of long-chain alkyl bromides is comparatively slow (entries 11,12, Table 1). In general, formation of sulfides took longer (1-4 h) than those of selenides (
