Pd(II)-Catalyzed Direct Olefination of Arenes with Allylic Esters and Ethers

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.

palladium catalysis - olefination - C-C bond formation - C-H bond activation - allylic ester

References and Notes

For representative reviews, see:

<A NAME="RW20611ST-1A">1a</A> Arndtsen BA. Bergman RG. Mobley TA. Peterson TH. Acc. Chem. Res.  1995,  28:  154 

<A NAME="RW20611ST-1B">1b</A> Dyker G. Angew. Chem. Int. Ed.  1999,  38:  1698 

<A NAME="RW20611ST-1C">1c</A> Jia C.-G. Kitamura T. Fujiwara Y. Acc. Chem. Res.  2001,  34:  633 

<A NAME="RW20611ST-1D">1d</A> Ritleng V. Sirlin C. Pfeffer M. Chem. Rev.  2002,  102:  1731 

<A NAME="RW20611ST-1E">1e</A> Kakiuchi F. Chatani N. Adv. Synth. Catal.  2003,  345:  1077 

<A NAME="RW20611ST-1F">1f</A> Godula K. Sames D. Science  2006,  312:  67 

<A NAME="RW20611ST-1G">1g</A> Bergman RG. Nature (London)  2007,  446:  391 

<A NAME="RW20611ST-1H">1h</A> Alberico D. Scott ME. Lautens M. Chem. Rev.  2007,  107:  174 

<A NAME="RW20611ST-1I">1i</A> Ackermann L. Vicente R. Kapdi AR. Angew. Chem. Int. Ed.  2009,  48:  9792 

<A NAME="RW20611ST-1J">1j</A> Chen X. Engle KM. Wang D.-H. Yu J.-Q. Angew. Chem. Int. Ed.  2009,  48:  5094 

<A NAME="RW20611ST-1K">1k</A> Thansandote P. Lautens M. Chem. Eur. J.  2009,  15:  5874 

<A NAME="RW20611ST-1L">1l</A> Li C.-J. Acc. Chem. Res.  2009,  42:  335 

<A NAME="RW20611ST-1M">1m</A> Daugulis O. Do H.-Q. Shabashov D. Acc. Chem. Res.  2009,  42:  1074 

<A NAME="RW20611ST-1N">1n</A> Dobereiner GE. Crabtree RH. Chem. Rev.  2010,  110:  681 

<A NAME="RW20611ST-1O">1o</A> Lyons TW. Sanford MS. Chem. Rev.  2010,  110:  1147 

<A NAME="RW20611ST-1P">1p</A> Zhang S.-Y. Zhang F.-M. Tu Y.-Q. Chem. Soc. Rev.  2011,  40:  1937 

<A NAME="RW20611ST-1Q">1q</A> Sun C.-L. Li B.-J. Shi Z.-J. Chem. Rev.  2011,  111:  1293 

<A NAME="RW20611ST-1R">1r</A> Li B.-J. Yang S.-D. Shi Z.-J. Synlett  2008,  949 

<A NAME="RW20611ST-1S">1s</A> Sun C.-L. Li B.-J. Shi Z.-J. Chem. Commun.  2010,  46:  677 

<A NAME="RW20611ST-2">2</A> For a very recent excellent review, see: Bras JL. Muzart J. Chem. Rev.  2011,  111:  1170 

<A NAME="RW20611ST-3A">3a</A> Moritani I. Fujiwara Y. Tetrahedron Lett.  1967,  8:  1119 

<A NAME="RW20611ST-3B">3b</A> Fujiwara Y. Moritani I. Danno S. Asano R. Teranishi S. J. Am. Chem. Soc.  1969,  91:  7166 

<A NAME="RW20611ST-3C">3c</A> Jia C. Piao D. Oyamada J. Lu W. Kitamura T. Fujiwara Y. Science  2000,  287:  1992 

<A NAME="RW20611ST-4A">4a</A> Yokota T. Tani M. Sakaguchi S. Ishii Y. J. Am. Chem. Soc.  2003,  125:  1476 

<A NAME="RW20611ST-4B">4b</A> Dams M. De Vos DE. Celen S. Jacobs PA. Angew. Chem. Int. Ed.  2003,  42:  3512 

<A NAME="RW20611ST-5A">5a</A> Zhang Y.-H. Shi B.-F. Yu J.-Q. J. Am. Chem. Soc.  2009,  131:  5072 

<A NAME="RW20611ST-5B">5b</A> Ye M.-C. Gao G.-L. Yu J.-Q. J. Am. Chem. Soc.  2011,  133:  6964 

<A NAME="RW20611ST-6">6</A> Zhang X. Fan S. He C.-Y. Wan X. Min Q.-Q. Yang J. Jiang Z.-X. J. Am. Chem. Soc.  2010,  132:  4506 

<A NAME="RW20611ST-7A">7a</A> Miura M. Tsuda T. Satoh T. Pivsa-Art S. Nomura M. J. Org. Chem.  1998,  63:  5211 

<A NAME="RW20611ST-7B">7b</A> Boele MDK. van Strijdonck GTPF. de Vries AHM. Kamer PCJ. de Vries JG. van Leeuwen PWNM. J. Am. Chem. Soc.  2002,  124:  1586 

<A NAME="RW20611ST-7C">7c</A> Zaitsev VG. Daugulis O. J. Am. Chem. Soc.  2005,  127:  4156 

<A NAME="RW20611ST-7D">7d</A> Wang J.-R. Yang C.-T. Liu L. Guo Q.-X. Tetrahedron Lett.  2007,  48:  5449 

<A NAME="RW20611ST-7E">7e</A> Cai G. Fu Y. Li Y. Wan X. Shi Z. J. Am. Chem. Soc.  2007,  129:  7666 

<A NAME="RW20611ST-7F">7f</A> Li J.-J. Mei T.-S. Yu J.-Q. Angew. Chem. Int. Ed.  2008,  47:  6452 

<A NAME="RW20611ST-7G">7g</A> Houlden CE. Bailey CD. Ford JG. Gagné MR. Lloyd-Jones GC. Booker-Milburn KI. J. Am. Chem. Soc.  2008,  130:  10066 

<A NAME="RW20611ST-7H">7h</A> Wang D.-H. Engle KM. Shi B.-F. Yu J.-Q. Science  2010,  327:  315 

<A NAME="RW20611ST-7I">7i</A> Park SH. Kim JY. Chang S. Org. Lett.  2011,  13:  2372 

<A NAME="RW20611ST-8">8</A> Cho SH. Hwang SJ. Chang S. J. Am. Chem. Soc.  2008,  130:  9254 

<A NAME="RW20611ST-9">9</A> Pan D. Jiao N. Synlett  2010,  1577 

<A NAME="RW20611ST-10A">10a</A> 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 

<A NAME="RW20611ST-10B">10b</A> Su YJ. Jiao N. Org. Lett.  2009,  11:  2980 

<A NAME="RW20611ST-10C">10c</A> Pan D. Yu M. Chen W. Jiao N. Chem. Asian J.  2010,  5:  1090 

<A NAME="RW20611ST-11">11</A>

The cinnamyl acetate was also generated in the absence of toluene when PdCl₂(Ph₃P)₂ was used as catalyst.

<A NAME="RW20611ST-12">12</A>

Typical 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.

<A NAME="RW20611ST-13A">13a</A> Bernocchi E. Cacchi S. Ciattini PG. Morera E. Ortar G. Tetrahedron Lett.  1992,  33:  3073 

<A NAME="RW20611ST-13B">13b</A> Kang S.-K. Lee H.-W. Jang S.-B. Kim T.-H. Pyun S.-J. J. Org. Chem.  1996,  61:  2604