Acetylation of N-Heteroaryl Bromides via PdCl2/(o-tolyl)3P Catalyzed Heck Reactions

Tianxiong He; Xiaochun Tao; Xinyan Wu; Lisheng Cai; Victor W. Pike

doi:10.1055/s-2008-1032193

PAPER

Acetylation of N-Heteroaryl Bromides via PdCl₂/(o-tolyl)₃P Catalyzed Heck Reactions

Tianxiong He^a, Xiaochun Tao*^a, Xinyan Wu^a, Lisheng Cai*^b, Victor W. Pike^b
^a Laboratory of Organometallic Chemistry, East China University of Science and Technology, Shanghai 200237, P. R. of China
^b Molecular Imaging Branch, National Institute of Mental Health, National Institutes of Health, Bethesda, MD 20892, USA
e-Mail: LishengCai@mail.nih.gov; e-Mail: xctao@ecust.edu.cn;

Abstract

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Abstract

A new user-friendly and convenient method for the acetylation of N-heteroaryl bromides is described. This process is based on the palladium-catalyzed olefination of an N-heteroaryl bromide with butyl vinyl ether, followed by acid hydrolysis of the intermediate heteroaryl vinyl ether in situ. Isopropanol at 85 °C, in the presence of K₃PO₄·3H₂O (2 equiv), PdCl₂ (2 mol%) and (o-tolyl)₃P (4 mol%), provided the best conditions, giving yields of N-heteroaryl bromides up to 75%.

Key words

acetylation - butyl vinyl ether - isopropanol - N-heteroaryl bromides

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References

<A NAME="RM08007SS-1">1</A> Cooper GH. Rickard RL. J. Chem. Soc. C 1971, 3257

<A NAME="RM08007SS-2">2</A> Edward JT. Mo YS. J. Heterocycl. Chem. 1973, 10: 1047

<A NAME="RM08007SS-3">3</A> Abarca B. Asensio A. Jones G. Mouat DJ. Tetrahedron 1989, 45: 7041

<A NAME="RM08007SS-4">4</A> Murray TJ. Zimmerman SC. Kolotuchin SV. Tetrahedron 1995, 51: 635

<A NAME="RM08007SS-5">5</A> Legros JY. Primault G. Fiaud JC. Tetrahedron 2001, 57: 2507

<A NAME="RM08007SS-6">6</A> Chan L. Jin H. Stefanac T. Lavallee JF. Falardeau G. Wang W. Bedard J. May S. Yuen L. J. Med. Chem. 1999, 42: 3023

<A NAME="RM08007SS-7">7</A> Bakke JM. Riha J. J. Heterocycl. Chem. 2001, 38: 99

<A NAME="RM08007SS-8">8</A> Katsura Y. Inoue Y. Tomishi T. Ishikawa H. Takasugi H. J. Med. Chem. 1994, 37: 57

<A NAME="RM08007SS-9">9</A> Matulenko MA. Lee CH. Jiang M. Frey RR. Cowart MD. Bayburt EK. DiDomenico S. Gfesser GA. Gomtsyan A. Zheng GZ. Mckie JA. Stewart AO. Yu HX. Kohlhaas KL. Alexander KM. McGaraughty S. Wismer CT. Mikusa J. Marsh KC. Snyder RD. Diehl MS. Kowaluk EA. Jarvis MF. Bhagwat SS. Bioorg. Med. Chem. 2005, 13: 3705

<A NAME="RM08007SS-10">10</A> Henke BR. Aquino CJ. Birkemo LS. Croom DK. Dougherty RW. Ervin GN. Grizzle MK. Hirst GC. James MK. Johnson MF. Queen KL. Sherrill RG. Sugg EE. Suh EM. Szewczyk JW. Unwalla RJ. Yingling J. Willson TM. J. Med. Chem. 1997, 40: 2706

<A NAME="RM08007SS-11">11</A> Wright SW. Hageman DL. McClure LD. J. Heterocycl. Chem. 1998, 35: 719

<A NAME="RM08007SS-12">12</A> Heck RF. Nolley JP. J. Org. Chem. 1972, 37: 2320

<A NAME="RM08007SS-13">13</A> Dieck HA. Heck RF. J. Am. Chem. Soc. 1974, 96: 1133

<A NAME="RM08007SS-14">14</A> Daves GD. Hallberg A. Chem. Rev. 1989, 89: 1433

<A NAME="RM08007SS-15">15</A> Berthiol F. Feuerstein M. Doucet H. Santelli M. Tetrahedron Lett. 2002, 43: 5625

<A NAME="RM08007SS-16">16</A> Battace A. Feuerstein M. Lemhadri M. Zair T. Doucet H. Santelli M. Eur. J. Org. Chem. 2007, 3122

<A NAME="RM08007SS-17">17</A> Pei W. Mo J. Xiao JL. J. Organomet. Chem. 2005, 690: 3546

<A NAME="RM08007SS-18">18</A> Liu SF. Berry N. Thomson N. Pettman A. Hyder Z. Mo J. Xiao JL. J. Org. Chem. 2006, 71: 7467

<A NAME="RM08007SS-19">19</A> Arvela RK. Pasquini S. Larhed M. J. Org. Chem. 2007, 72: 6390

<A NAME="RM08007SS-20X">20x</A> Tao X. Zhang Y. Shen D. Chin. J. Chem. 2007, 25: 1326

<A NAME="RM08007SS-20">20</A> Amatore C. Godin B. Jutand A. Lemaitre F. Organometallics 2007, 26: 1757

<A NAME="RM08007SS-21">21</A> Jeffery T. Tetrahedron 1996, 52: 10113

<A NAME="RM08007SS-22">22</A> Amatore C. Jutand A. Acc. Chem. Res. 2000, 33: 314

<A NAME="RM08007SS-23">23</A> Mo J. Xiao JL. Angew. Chem. Int. Ed. 2006, 45: 4152

<A NAME="RM08007SS-24">24</A> Ohff M. Ohff A. van der Boom ME. Milstein D. J. Am. Chem. Soc. 1997, 119: 11687

<A NAME="RM08007SS-25">25</A> Beller M. Riermeier TH. Eur. J. Inorg. Chem. 1998, 29

<A NAME="RM08007SS-26">26</A> Nalesnik TE. Holy NL. J. Org. Chem. 1977, 42: 372

<A NAME="RM08007SS-27">27</A> Blackburn TF. Schwartz J. J. Chem. Soc., Chem. Commun. 1977, 157

<A NAME="RM08007SS-28">28</A> Bellosta V. Benhaddou R. Czernecki S. Synlett 1993, 861

<A NAME="RM08007SS-29">29</A> Singh R. Viciu MS. Kramareva N. Navarro O. Nolan SP. Org. Lett. 2005, 7: 1829

<A NAME="RM08007SS-30">30</A> Akagi M. Ozaki K. Heterocycles 1987, 26: 61

<A NAME="RM08007SS-31">31</A> Somei M. Natsume M. Tetrahedron Lett. 1973, 2451

<A NAME="RM08007SS-32">32</A> Yang YH. Martin AR. Nelson DL. Regan J. Heterocycles 1992, 34: 1169