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DOI: 10.1055/s-2007-986662
Palladium-Catalyzed Reductive Carbonylation of Aryl Triflates with Synthesis Gas
Publikationsverlauf
Publikationsdatum:
12. September 2007 (online)
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Abstract
A general palladium-catalyzed reductive carbonylation of aryl triflates in the presence of synthesis gas (CO/H2) has been developed. The reaction with this most simple and environmentally benign formylation source proceeds under mild conditions and various aromatic aldehydes have been prepared in good to high yield.
Key words
carbonylation - palladium - aryl triflates - aldehydes - homogenous catalysis
-
1a
Frenette R.Hutchinson JH.Léger S.Thérien M.Brideau C.Chan CC.Charleson S.Ethier D.Guay J.Jones TR.McAuliffe M.Piechutta H.Riendeau D.Tagari P.Girard Y. Bioorg. Med. Chem. Lett. 1999, 9: 2391 -
1b
Henley PD.Kilburn JD. Chem. Commun. 1999, 1335 -
1c
Miller WH.Bondinell WE.Cousins RD.Erhard KF.Jakas DR.Keenan RM.Ku TW.Newlander KA.Ross ST.Haltiwanger RC.Bradbeer J.Drake FH.Gowen M.Hoffman SJ.Hwang S.-M.James IE.Lark MW.Lechowska B.Rieman DJ.Stroup GB.Vasko-Moser JA.Zembryki DL.Azzarano LM.Adams PC.Salyers KL.Smith BR.Ward KW.Johanson KO.Huffman WF. Bioorg. Med. Chem. Lett. 1999, 9: 1807 -
1d
Xiang AX.Watson DA.Ling T.Theodorakis EA. J. Org. Chem. 1998, 63: 6774 -
1e
Wang L.Shen W. Tetrahedron Lett. 1998, 39: 7625 -
1f
Ma D.Tian H.Sun H.Kozikowski AP.Pshenichkin S.Wroblewski JT. Bioorg. Med. Chem. Lett. 1997, 7: 1195 -
1g
Fretz H. Tetrahedron Lett. 1996, 37: 8475 -
1h
Shishido K.Goto K.Miyoshi S.Takaishi Y.Shibuya M. J. Org. Chem. 1994, 59: 406 -
1i
Thompson SK.Heathcock CH. J. Org. Chem. 1992, 57: 5979 -
2a
Lesma G.Sacchetti A.Silvani A. Synthesis 2006, 594 -
2b
Cacchi S.Fabrizi G.Goggiamani A. Org. Lett. 2003, 5: 4269 -
2c
Cacchi S.Lupi A. Tetrahedron Lett. 1992, 33: 3939 -
3a
Iwamoto H.Yukimasa Y.Fukazawa Y. Tetrahedron Lett. 2002, 43: 8191 -
3b
Lin S.-K.Rasetti V. Helv. Chim. Acta 1995, 78: 857 -
3c
Kraus GA.Maeda H. Tetrahedron Lett. 1994, 35: 9189 -
3d
Ohta T.Ito M.Inagaki K.Takaya H. Tetrahedron Lett. 1993, 34: 1615 -
3e
Dolle RE.Schmidt SJ.Kruse LI. J. Chem. Soc., Chem. Commun. 1987, 904 - 4
Cacchi S.Ciattini PG.Morera E.Ortar G. Tetrahedron Lett. 1986, 27: 3931 - 5
Baillargeon VP.Stille JK. J. Am. Chem. Soc. 1986, 108: 452 -
6a
Hashimoto A.Shi Y.Drake K.Koh JT. Bioorg. Med. Chem. 2005, 13: 3627 -
6b
Hennequin LFA, andHalsall CT. inventors; WO 026156. -
6c
Nemoto T.Ohshima T.Shibasaki M. Tetrahedron 2003, 59: 6889 -
6d
Morera E.Ortar G.Varani A. Synth. Commun. 1998, 28: 4279 -
6e
Kotsuki H.Datta PK.Suenaga H. Synthesis 1996, 470 - 7
Holzapfel CW.Ferreira AC.Marais W. J. Chem. Res. 2002, 5: 218 - 8 For a personal account, see:
Zapf A.Beller M. Chem. Commun. 2005, 431 - See, for example:
-
9a
Harkal S.Rataboul F.Zapf A.Fuhrmann C.Riermeier TH.Monsees A.Beller M. Adv. Synth. Catal. 2004, 346: 1742 -
9b
Harkal S.Michalik D.Zapf A.Jackstell R.Rataboul F.Riermeier TH.Monsees A.Beller M. Tetrahedron Lett. 2005, 46: 3237 - 10
Ehrentraut A.Zapf A.Beller M. Synlett 2000, 1589 - 11
Zapf A.Ehrentraut A.Beller M. Angew. Chem. Int. Ed. 2000, 39: 4153 -
12a
Tewari A.Hein M.Zapf A.Beller M. Tetrahedron 2005, 61: 9705 -
12b
Ehrentraut A.Zapf A.Beller M. J. Mol. Catal. 2002, 182-183: 515 - 13
Schareina T.Zapf A.Mägerlein W.Müller N.Beller M. Tetrahedron Lett. 2007, 48: 1087 - 14
Ehrentraut A.Zapf A.Beller M. Adv. Synth. Catal. 2002, 344: 209 - 15
Klaus S.Neumann H.Zapf A.Strübing D.Hübner S.Almena J.Riermeier TH.Groß P.Sarich R.Krahnert W.-R.Rossen K.Beller M. Angew. Chem. Int. Ed. 2006, 45: 154 - 16
Neumann H.Brennführer A.Groß P.Riermeier TH.Almena J.Beller M. Adv. Synth. Catal. 2006, 348: 1255 - 17 Aryl triflates were prepared from the corresponding phenols by a well-established method:
Echavarren AM.Stille JK. J. Am. Chem. Soc. 1987, 109: 5478 - For previous work on palladium-catalyzed carbonylations of aryl halides applying CO, see for example:
-
19a
Ashfield L.Barnard CFJ. Org. Process Res. Dev. 2007, 11: 39 -
19b
Cai M.-Z.Zhao H.Zhou J.Song C.-S. Synth. Commun. 2002, 32: 923 -
19c
Schnyder A.Beller M.Mehltretter G.Nsenda T.Studer M.Indolese AF. J. Org. Chem. 2001, 66: 4311 -
19d
Bates RW.Gabel CJ.Ji J.Rama-Devi T. Tetrahedron 1995, 51: 8199 -
19e
Hartman GD.Halczenko W. Synth. Commun. 1991, 21: 2103 -
19f
Mutin R.Lucas C.Thivolle-Cazat J.Dufaud V.Dany F.Basset JM. J. Chem. Soc., Chem. Commun. 1988, 896 - 19g See ref. 5
-
19h
Pri-Bar I.Buchman O. J. Org. Chem. 1984, 49: 4009 -
19i
Baillargeon VP.Stille JK. J. Am. Chem. Soc. 1983, 105: 7175 -
19j
Schoenberg A.Heck RF. J. Am. Chem. Soc. 1974, 96: 7761
References and Notes
A 50 mL round-bottom flask was charged with 4-methoxy-phenol (1.86 g, 15 mmol) and sealed with a septum. Subsequently, pyridine (15 mL) was added. The clear solution was cooled to 0 °C and trifluoromethanesulfonic anhydride (2.8 mL, 17 mmol) was added dropwise. The resulting orange solution was stirred over night at r.t. Another 10 mL Schlenk flask was charged with Pd(OAc)2 (50.5 mg, 1.5 mol%), 1,3-bis(diphenylphosphino)propane (139.2 mg, 2.25 mol%), DMF (5 mL), and 2-butoxyethyl ether (2.61 mL, internal GC standard). Both solutions were combined and transferred to a 100 mL autoclave of the 4560 series from Parr Instruments® under argon atmosphere. After flushing the autoclave three times with CO/H2 (1:1), 20 bar of synthesis gas were adjusted at ambient temperature and the reaction was performed for 24 h at 100 °C. Before and after the reductive carbonylation an aliquot of the reaction mixture was subjected to GC analysis for determination of yield and conversion.