Subscribe to RSS
DOI: 10.1055/s-2005-865195
The First Example of Polymer-Supported Palladium Catalyst for Stereoselective S-S Bond Addition to Terminal Alkynes
Publication History
Publication Date:
23 March 2005 (online)
![](https://www.thieme-connect.de/media/synlett/200506/lookinside/thumbnails/10.1055-s-2005-865195-1.jpg)
Abstract
The polymer-supported recyclable palladium catalyst was prepared for stereoselective diaryl disulphides addition to terminal alkynes with high yields. The 96-98% product purity was achieved after filtering the polymer-supported catalyst without special purification procedure.
Key words
palladium complexes - polymer-supported - catalysis - vinyl sulphides
-
1a
Anastas PT.Kirchhoff MM. Acc. Chem. Res. 2002, 35: 686 -
1b
Trost BM. Acc. Chem. Res. 2002, 35: 695 -
1c
Wulff G. Chem. Rev. 2002, 102: 1 -
1d
Bergbreiter DE. Chem. Rev. 2002, 102: 3345 -
1e
Anastas PT.Kirchhoff MM.Williamson TC. Appl. Catal. A. 2001, 221: 3 -
2a
Benaglia M.Puglisi A.Cozzi F. Chem. Rev. 2003, 103: 3401 -
2b
Leadbeater NE.Marco M. Chem. Rev. 2002, 102: 3217 -
2c
Gilbertson SR.Yamada S. Tetrahedron Lett. 2004, 45: 3917 -
3a
Kuniyasu H.Ogawa A.Miyazaki S.-I.Ryu I.Kambe N.Sonoda N. J. Am. Chem. Soc. 1991, 113: 9796 -
3b
Ogawa A. J. Organomet. Chem. 2000, 611: 463 - For general reviews on the catalytic E-E bond addition to alkynes see:
-
4a
Catalytic Heterofunctionalization
Togni A.Grutzmacher H. Wiley-VCH; Weinheim: 2001. -
4b
Beletskaya I.Moberg C. Chem. Rev. 1999, 99: 3435 -
5a
Ananikov VP.Kabeshov MA.Beletskaya IP.Aleksandrov GG.Eremenko IL. J. Organomet. Chem. 2003, 687: 451 -
5b
Ananikov VP.Beletskaya IP.Aleksandrov GG.Eremenko IL. Organometallics 2003, 22: 1414 -
5c
Ananikov VP.Beletskaya IP. Org. Biomol. Chem. 2004, 2: 284 -
6a
The Chemistry of Organic Selenium and Tellurium Compounds
Vol. 1-2:
Patai S.Rappoport Z. John Wiley and Sons; New York: 1986. -
6b
Kondo T.Mitsudo T. Chem. Rev. 2000, 100: 3205 -
6c
Zyk NV.Beloglazkina EK.Belova MA.Dubinina NS. Russ. Chem. Rev. 2003, 72: 769 - 7
Hope EG.Levason W. Coord. Chem. Rev. 1993, 122: 109 - 8
Clemenson PI. Coord. Chem. Rev. 1990, 106: 171 - 9
Lauterbach C.Fabian J. Eur. J. Inorg. Chem. 1999, 1995
References
The triphenylphosphine resin 100-200 mesh, 1% DVB, 1-1.5 mmol/g was used as a polymeric ligand (ACROS organics, catalog No 35833).
11Catalyst Preparation. The Ar2S2 (0.2 mmol), PPh3 resin (0.069 mmol, 1.25 mmol PPh3/g, 0.055 g), Pd2dba3 (3.4 × 10-3 mmol, 3 mg), and 0.5 mL of degassed toluene were stirred at 140 °C for 30 min in a sealed tube. The mixture was cooled to the r.t., polymer-supported catalyst was filtered and washed thrice with 2 mL of degassed toluene (all manipulations were performed under argon). The formation of polymer-supported palladium catalyst is accompanied with releasing free dba ligand (confirmed by NMR). Washing with toluene removes dba from the catalyst. The presence of Ar2S2 on the catalyst preparation stage is important, since oxidative addition of Ar2S2 converts Pd(0) to Pd(II), which is more stable and easier to handle.
12
General Synthetic Procedure.
The Ar2S2 (0.3 mmol), the alkyne (0.45 mmol) and 1 mL of degassed toluene were combined with the polymer-supported catalyst and the mixture was stirred at 140 °C for 2 h in a sealed tube. The solution was separated and the polymer-supported catalyst was washed twice with 2 mL of degassed toluene. Combined organic solution was evaporated and dried under reduced pressure. The 2A-2H products (96-98% purity) were obtained as yellow oil. Unreacted alkyne was removed with a solvent upon evaporation. Otherwise (for 2I and 2J) flash chromato-graphy was needed to separate unreacted alkynes. The products 2A-2G were identified according to the published NMR data (see ref. 3,5). The data for the 2-H, 2-I and 2-J is given below.
Z-CH(SPh)=C(SPh)-CH2CH2CH2CN (2-H): yellow oil. 1H NMR (500 MHz, CDCl3): δ = 1.78-1.85 (m, 2 H, CH2), 2.27 (t, 2 H, CH2), 2.40 (t, 2 H, CH2), 6.68 (s, 1 H, HC=), 7.20-7.38 (m, 8 H, Ph), 7.40-7.45 (m, 2 H, Ph) ppm. 13C{1H} NMR (126 MHz, CDCl3): δ = 15.9, 23.9, 35.2, 119.1 (CN), 127.1, 127.2, 129.1, 129.2, 130.0, 130.2, 130.5, 132.4 (HC=), 132.9, 135.0 ppm. MS (EI): m/e (%) = 311 (60) [M+]. Anal. Calcd for C18H17NS2: C, 69.41; H, 5.50; N, 4.50. Found: C, 69.35; H, 5.80; N, 4.40.
Z-HC(SPh)=C(SPh)-CH2SPh (2-I): yellow oil. 1H NMR (500 MHz, CDCl3): δ = 3.65 (s, 2 H, CH2), 6.70 (s, 1 H, HC=), 7.13-7.17 (m, 2 H, Ph), 7.20-7.33 (m, 11 H, Ph), 7.35-7.39 (m, 2 H, Ph) ppm. 13C{1H} NMR (126 MHz, CDCl3): δ = 41.3 (CH2), 126.8, 127.0, 127.1, 127.4, 128.9, 129.0, 129.1, 129.8, 130.7, 131.1, 133.1, 134.1 (HC=), 135.0, 135.1 ppm. MS (EI): m/e (%) = 366 (20) [M+]. Anal. Calcd for C21H18S3: C, 68.81; H, 4.95; S, 26.24. Found: C, 68.90; H, 5.00; S, 26.50.
Z-HC(SPh)=C(SPh)-CH2SePh (2-J): yellow oil. 1H NMR (500 MHz, CDCl3): δ = 3.68 (s, 2 H, CH2), 6.48 (s, 1 H, HC=), 7.13-7.17 (m, 2 H, Ph), 7.20-7.35 (m, 9 H, Ph), 7.38-7.42 (m, 2 H, Ph), 7.48-7.52 (m, 2 H, Ph) ppm. 13C{1H} NMR (126 MHz, CDCl3): δ = 35.2 (CH2), 127.0, 127.1, 127.7, 128.6, 128.9, 129.0, 129.1, 129.6, 129.9, 130.6, 133.2, 133.3, 134.6, 135.0 ppm. MS (EI): m/e (%) = 414 (70) [M+]. Anal. Calcd for C21H18S2Se: C, 61.00; H, 4.39; S, 15.51; Se, 19.10. Found: C, 60.81; H, 4.33; S, 15.56; Se, 19.10.
Catalyst Recycling. After washing with toluene (see general synthetic procedure [12] ) the polymer-supported catalyst can be used in further reactions without additional treatment. When recycling, all manipulations with the catalyst should be performed under argon.