Subscribe to RSS
DOI: 10.1055/s-0031-1290078
Pd(II)-Catalyzed Direct Olefination of Arenes with Allylic Esters and Ethers
Publication History
Publication Date:
03 January 2012 (online)

Abstract
A convenient Pd(II)-catalyzed direct olefination of unactivated arenes with allylic esters and ethers via C-H activation was demonstrated. Under the typical conditions, various aryl-substituted allylic esters and ethers can be prepared.
Key words
palladium catalysis - olefination - C-C bond formation - C-H bond activation - allylic ester
- Supporting Information for this article is available online:
- Supporting Information
- For representative reviews, see:
- 1a
Arndtsen BA.Bergman RG.Mobley TA.Peterson TH. Acc. Chem. Res. 1995, 28: 154 - 1b
Dyker G. Angew. Chem. Int. Ed. 1999, 38: 1698 - 1c
Jia C.-G.Kitamura T.Fujiwara Y. Acc. Chem. Res. 2001, 34: 633 - 1d
Ritleng V.Sirlin C.Pfeffer M. Chem. Rev. 2002, 102: 1731 - 1e
Kakiuchi F.Chatani N. Adv. Synth. Catal. 2003, 345: 1077 - 1f
Godula K.Sames D. Science 2006, 312: 67 - 1g
Bergman RG. Nature (London) 2007, 446: 391 - 1h
Alberico D.Scott ME.Lautens M. Chem. Rev. 2007, 107: 174 - 1i
Ackermann L.Vicente R.Kapdi AR. Angew. Chem. Int. Ed. 2009, 48: 9792 - 1j
Chen X.Engle KM.Wang D.-H.Yu J.-Q. Angew. Chem. Int. Ed. 2009, 48: 5094 - 1k
Thansandote P.Lautens M. Chem. Eur. J. 2009, 15: 5874 - 1l
Li C.-J. Acc. Chem. Res. 2009, 42: 335 - 1m
Daugulis O.Do H.-Q.Shabashov D. Acc. Chem. Res. 2009, 42: 1074 - 1n
Dobereiner GE.Crabtree RH. Chem. Rev. 2010, 110: 681 - 1o
Lyons TW.Sanford MS. Chem. Rev. 2010, 110: 1147 - 1p
Zhang S.-Y.Zhang F.-M.Tu Y.-Q. Chem. Soc. Rev. 2011, 40: 1937 - 1q
Sun C.-L.Li B.-J.Shi Z.-J. Chem. Rev. 2011, 111: 1293 - 1r
Li B.-J.Yang S.-D.Shi Z.-J. Synlett 2008, 949 - 1s
Sun C.-L.Li B.-J.Shi Z.-J. Chem. Commun. 2010, 46: 677 - 2 For a very recent excellent review,
see:
Bras JL.Muzart J. Chem. Rev. 2011, 111: 1170 - 3a
Moritani I.Fujiwara Y. Tetrahedron Lett. 1967, 8: 1119 - 3b
Fujiwara Y.Moritani I.Danno S.Asano R.Teranishi S. J. Am. Chem. Soc. 1969, 91: 7166 - 3c
Jia C.Piao D.Oyamada J.Lu W.Kitamura T.Fujiwara Y. Science 2000, 287: 1992 - 4a
Yokota T.Tani M.Sakaguchi S.Ishii Y. J. Am. Chem. Soc. 2003, 125: 1476 - 4b
Dams M.De Vos DE.Celen S.Jacobs PA. Angew. Chem. Int. Ed. 2003, 42: 3512 - 5a
Zhang Y.-H.Shi B.-F.Yu J.-Q. J. Am. Chem. Soc. 2009, 131: 5072 - 5b
Ye M.-C.Gao G.-L.Yu J.-Q. J. Am. Chem. Soc. 2011, 133: 6964 - 6
Zhang X.Fan S.He C.-Y.Wan X.Min Q.-Q.Yang J.Jiang Z.-X. J. Am. Chem. Soc. 2010, 132: 4506 - 7a
Miura M.Tsuda T.Satoh T.Pivsa-Art S.Nomura M. J. Org. Chem. 1998, 63: 5211 - 7b
Boele MDK.van Strijdonck GTPF.de Vries AHM.Kamer PCJ.de Vries JG.van Leeuwen PWNM. J. Am. Chem. Soc. 2002, 124: 1586 - 7c
Zaitsev VG.Daugulis O. J. Am. Chem. Soc. 2005, 127: 4156 - 7d
Wang J.-R.Yang C.-T.Liu L.Guo Q.-X. Tetrahedron Lett. 2007, 48: 5449 - 7e
Cai G.Fu Y.Li Y.Wan X.Shi Z. J. Am. Chem. Soc. 2007, 129: 7666 - 7f
Li J.-J.Mei T.-S.Yu J.-Q. Angew. Chem. Int. Ed. 2008, 47: 6452 - 7g
Houlden CE.Bailey CD.Ford JG.Gagné MR.Lloyd-Jones GC.Booker-Milburn KI. J. Am. Chem. Soc. 2008, 130: 10066 - 7h
Wang D.-H.Engle KM.Shi B.-F.Yu J.-Q. Science 2010, 327: 315 - 7i
Park SH.Kim JY.Chang S. Org. Lett. 2011, 13: 2372 - 8
Cho SH.Hwang SJ.Chang S. J. Am. Chem. Soc. 2008, 130: 9254 - 9
Pan D.Jiao N. Synlett 2010, 1577 - 10a
Pan D.Chen A.Su Y.Zhou W.Li S.Jia W.Xiao J.Liu Q.Zhang L.Jiao N. Angew. Chem. Int. Ed. 2008, 47: 4729 - 10b
Su YJ.Jiao N. Org. Lett. 2009, 11: 2980 - 10c
Pan D.Yu M.Chen W.Jiao N. Chem. Asian J. 2010, 5: 1090 - 13a
Bernocchi E.Cacchi S.Ciattini PG.Morera E.Ortar G. Tetrahedron Lett. 1992, 33: 3073 - 13b
Kang S.-K.Lee H.-W.Jang S.-B.Kim T.-H.Pyun S.-J. J. Org. Chem. 1996, 61: 2604
References and Notes
The cinnamyl acetate was also generated in the absence of toluene when PdCl2(Ph3P)2 was used as catalyst.
12Typical Procedure A mixture of mesitylene (1.9 mL, as solvent), allyl acetate (0.6 mmol, 60 mg), Pd(OAc)2 (0.06 mmol), AgOAc (1.2 mmol), and DMSO (0.1 mL) was added to a round-bottom flask. After stirring for 12 h at 110 ˚C, the solvent was removed under reduced pressure, and the residue was purified by flash chromatography on silica gel (eluent: PE-EtOAc = 20:1) to afford (E)-3-mesitylallyl acetate (73 mg, 56%) as a colorless oil. ¹H NMR (400 MHz, CDCl3): δ = 6.88 (s, 2 H), 6.64 (d, J = 16.0 Hz, 1 H), 5.84-5.76 (m, J = 16.0, 6.4 Hz, 1 H), 4.76 (dd, J = 6.4, 1.2 Hz, 2 H), 2.28 (s, 9 H), 2.12 (s, 3 H). ¹³C NMR (100 MHz, CDCl3): δ = 170.8, 136.4, 135.8, 132.9, 131.9, 128.6, 128.5, 65.4, 21.0, 20.9, 20.8, 20.7. HRMS: m/z calcd for C14H18NaO2: 241.1199; found: 241.1197.