A convenient method to remove ruthenium byproducts from olefin metathesis reactions using polymer-bound triphenylphosphine oxide (TPPO)

Molecular Diversity

Volumn 9, Issue 4, 2005, Pages 301-303

  Haack, KyoungLang ^a   Ahn, Yu Mi ^a   Georg, Gunda I ^a  

^a UNIVERSITY OF KANSAS   (United States)

Author keywords

Dimethyl sulfoxide; Polymer bound triphenylphosphine oxide; Ring closing metathesis; Ruthenium byproducts; Silica gel

Indexed keywords

ALKENE; DIMETHYL SULFOXIDE; POLYMER; RUTHENIUM; SILICA GEL; TOLUENE; TRIPHENYLPHOSPHINE; TRIPHENYLPHOSPHINE OXIDE; UNCLASSIFIED DRUG;

ARTICLE; CHEMICAL REACTION; PRIORITY JOURNAL; PRODUCTIVITY; RECYCLING; RING CLOSING METATHESIS; ROOM TEMPERATURE;

ALKENES; DIMETHYL SULFOXIDE; MODELS, CHEMICAL; ORGANOPHOSPHORUS COMPOUNDS; POLYMERS; RUTHENIUM; SILICON DIOXIDE;

EID: 28344437268     PISSN: 13811991     EISSN: None     Source Type: Journal    
DOI: 10.1007/s11030-005-2480-6     Document Type: Article

References (16)

1. Grubbs, R.H. and Chang, S., Recent advances in the Olefin metathesis and its application in organic synthesis, Tetrahedron, 54 (1998) 4413-4450.
2. 2 * Ru = CHR olefin metathesis catalysts: An organometallic success story, Acc. Chem. Res., 34 (2001) 18-29.
3. Fürstner, A., Olefin metathesis and beyond, Angew. Chem., 39 (2000) 3012-3043.
4. Schuster, M. and Blechert, S., Olefin metathesis in organic chemistiy, Angew. Chem., Int. Ed. Engl., 36 (1997) 2036-2056.
5. Schrock, R.R., Olefin Metathesis by Well-Defined Complexes of Molybdenum and Tungsten. Topics in Organometallic Chemistry. Alkene Methathesis in Organic Synthesis, Springer, Berlin, 1998, pp. 1-36.
6. Cho, J.H. and Kim, B.M., An efficient method for removal of ruthenium byproducts from olefin metathesis reactions, Org. Lett., 5 (2003) 531-533.
7. Maynard, H.D. and Grubbs, R.H., Purification technique for the removal of ruthenium from olefin metathesis reaction products, Tetrahedron Lett., 40 (1999) 4137-4140.
8. Paquette, L.A., Schloss, J.D., Efremov, I., Fabris, F., Gallou, F., Mendez-Andino, J. and Yang, J., A convenient method for removing all highly-colored byproducts generated during olefin metathesis reactions, Org. Lett., 2 (2000) 1259-1261.
9. Ahn, Y.M., Yang, K., and Georg, G.I., A convenient method for the efficient removal of ruthenium by-products generated during olefin metathesis reactions using triphenylphosphine oxide or dimethyl sulfoxide, Org. Lett., 3 (2001) 1411-1413.
10. Regen, S.L. and Lee, D.P., Solid phase phosphorus reagents, conversion of alcohols to. Alkyl Chlorides, J. Org. Chem., 40 (1975) 1669-1670. Polymer-supported TPP, cross-linked with 2% DVB, ∼3mmol P/g resin, was purchased from Aldrich.
11. Pouchert, C.J., The Aldrich Library of FT-IR Spectra, 1st Ed.; Vol 2. TPP: FT-IR 1(2), 539D: TPPO: FT-IR 1(2), 559A.
12. 31P MAS NMR, J. Comb. Chem., 5 (2003) 610-616.
13. 31P MAS NMR, Tetrahedron Lett., 44 (2003) 6987-6990.
14. Evidence that DMSO might destroy the ruthenium catalyst comes from Liras' work, who reported that a molecule bearing the sulfoxide functionality required the full equivalency of the Grubbs catalyst to drive the RCM reaction to completion. Liras, S., Davoren, J.E., and Bordner, J., An approach to the skeleton of the securinega alkaloids. The total synthesis of (±)-Securinine, Org. Lett., 3 (2001) 703-706.
15. 2 (40 mL) was added catalyst 1 (5 mol%). The mixture was stirred for 2 h and then the solvent was removed under reduced pressure. To the crude products toluene (5 mL), resin-bound TPPO (50 equiv, 145 mg) and DMSO (0.03 mL) were added, followed by heating for 6 h. The mixture was loaded on 1.8 g of silica gel for flash column chromatography and was eluted with 20% EtOAc in hexanes. Procedure for entries 6-10: To the crude products in toluene (5 mL), DMSO (0.03 mL), resin-bound TPPO (50 equiv, 45 mg) and silica gel (1.8 g) were added, followed by heating for 6 h. The mixture was filtered through a cotton-blocked pipette using 20% EtOAc in hexane.
16. The catalyst batch used in the experiments in Tables 1-3 was purchased from Strem. The additional experiments were carried out with a batch of catalyst purchased from Aldrich.