Room-Temperature Palladium-Catalyzed and Copper(I)-Mediated Coupling Reactions of Acid Chlorides with Boronic Acids under Neutral Conditions

Abstract

The palladium-catalyzed cross-coupling reactions of acid chlorides with arylboronic acids in the presence of copper(I) thiophene-2-carboxylate (CuTC) as an activator under strictly non-basic and mild reaction conditions afford the unsymmetrical ­ketones in moderate to excellent yields. A wide range of substrates bearing an electron-donating or an electron-withdrawing substi­tuent on the aromatic ring is compatible.

palladium - cross-coupling reaction - boronic acid - ­copper - ketones

References

<A NAME="RU19305ST-1">1</A> Review: Dieter RK. Tetrahedron  1999,  55:  4177 

<A NAME="RU19305ST-2">2</A> O’Neill BT. In Comprehensive Organic Synthesis   Vol. 1:  Trost BM. Fleming I. Pergamon; Oxford: 1991.  p.397-458  

<A NAME="RU19305ST-3A">3a</A> Miyaura N. Yamada K. Suzuki A. Tetrahedron Lett.  1979,  20:  3437 

For reviews on the Suzuki-Miyaura coupling, see:

<A NAME="RU19305ST-3B">3b</A> Suzuki A. Acc. Chem. Res.  1982,  15:  178 

<A NAME="RU19305ST-3C">3c</A> Suzuki A. Pure Appl. Chem.  1994,  66:  213 

<A NAME="RU19305ST-3D">3d</A> Miyaura N. Suzuki A. Chem. Rev.  1995,  95:  2457 

<A NAME="RU19305ST-3E">3e</A> Miyaura N. J. Organomet. Chem.  2002,  653:  54 

<A NAME="RU19305ST-3F">3f</A> Suzuki A. J. Organomet. Chem.  2002,  653:  83 

<A NAME="RU19305ST-3G">3g</A> Kotha S. Lahiri K. Kashinath D. Tetrahedron  2002,  58:  9633 

<A NAME="RU19305ST-3H">3h</A> Miyaura N. Top. Curr. Chem.  2002,  219:  1 

<A NAME="RU19305ST-4">4</A> Ishiyama T. Miyaura N. Suzuki A. Bull. Chem. Soc. Jpn.  1991,  64:  1999 

For recent reviews on cross-coupling, see:

<A NAME="RU19305ST-5A">5a</A> Tsuji J. Palladium Reagents and Catalysts   Wiley; Chichester U.K.: 1995.  p.290-422  

<A NAME="RU19305ST-5B">5b</A> Metal-catalyzed Cross-coupling Reactions   Diederich F. Stang PJ. Wiley-VCH; Weinheim: 1998. 

<A NAME="RU19305ST-5C">5c</A> Hassan J. Sevignon M. Gozzi C. Schulz E. Lemaire M. Chem. Rev.  2002,  102:  1359 

<A NAME="RU19305ST-6">6</A> Zapf A. Angew. Chem. Int. Ed.  2003,  42:  5394 ; and references cited therein

<A NAME="RU19305ST-7A">7a</A> Gooßen LJ. Ghosh K. Angew. Chem. Int. Ed.  2001,  40:  3458 

<A NAME="RU19305ST-7B">7b</A> Gooßen LJ. Ghosh K. Chem. Commun.  2001,  20:  2084 

<A NAME="RU19305ST-7C">7c</A> Gooßen LJ. Winkel L. Dohring A. Ghosh K. Paetzold J. Synlett  2002,  1237 

<A NAME="RU19305ST-7D">7d</A> Gooßen LJ. Ghosh K. Eur. J. Org. Chem.  2002,  3254 

<A NAME="RU19305ST-8A">8a</A> Kakino R. Narahashi H. Shimizu I. Yamamoto A. Chem. Lett.  2001,  12:  1242 

<A NAME="RU19305ST-8B">8b</A> Kakino R. Narahashi H. Shimizu I. Yamamoto A. Bull. Chem. Soc. Jpn.  2002,  75:  1333 

<A NAME="RU19305ST-9A">9a</A> Kakino R. Shimizu I. Yamamoto A. Bull. Chem. Soc. Jpn.  2001,  74:  371 

<A NAME="RU19305ST-9B">9b</A> Kakino R. Yasumi S. Shimizu I. Yamamoto A. Bull. Chem. Soc. Jpn.  2002,  75:  137 

<A NAME="RU19305ST-10">10</A> Tatamidani H. Kakiuchi F. Chatani N. Org. Lett.  2004,  6:  3597 

<A NAME="RU19305ST-11">11</A> Zeysing B. Gosch C. Terfort A. Org. Lett.  2000,  2:  1843 

<A NAME="RU19305ST-12A">12a</A> Savarin C. Srogl J. Liebeskind LS. Org. Lett.  2000,  2:  3229 

<A NAME="RU19305ST-12B">12b</A> Liebeskind LS. Srogl J. J. Am. Chem. Soc.  2000,  122:  11260 

<A NAME="RU19305ST-12C">12c</A> Yu Y. Liebeskind LS. J. Org. Chem.  2004,  69:  3554 

<A NAME="RU19305ST-13A">13a</A> Cho CS. Itotani K. Uemura S. J. Organomet. Chem.  1993,  443:  253 

<A NAME="RU19305ST-13B">13b</A> Kabalka GW. Malladi RR. Tejedor D. Kelley S. Tetrahedron Lett.  2000,  41:  999 

<A NAME="RU19305ST-13C">13c</A> Wang J.-X. Wei B. Hu Y. Liu Z. Yang Y. Synth. Commun.  2001,  31:  3885 

<A NAME="RU19305ST-14A">14a</A> Haddach M. McCarthy JR. Tetrahedron Lett.  1999,  40:  3109 

<A NAME="RU19305ST-14B">14b</A> Bumagin NA. Korolev DN. Tetrahedron Lett.  1999,  40:  3057 

<A NAME="RU19305ST-14C">14c</A> Chen H. Deng M.-Z. Org. Lett.  2000,  2:  1649 

<A NAME="RU19305ST-14D">14d</A> Urawa Y. Ogura K. Tetrahedron Lett.  2003,  44:  271 

<A NAME="RU19305ST-14E">14e</A> Urawa Y. Nishiura K. Souda S. Ogura K. Synthesis  2003,  2882 

<A NAME="RU19305ST-15">15</A> Zhang S. Zhang D. Liebeskind LS. J. Org. Chem.  1997,  62:  2312 

<A NAME="RU19305ST-16">16</A> Yamashita H. Kobayashi T. Sakakura T. Tanaka M. J. Organomet. Chem.  1988,  356:  125 

<A NAME="RU19305ST-17A">17a</A> Brumbaugh JS. Whittle RR. Parvez M. Sen A. Organometallics  1990,  9:  1735 

<A NAME="RU19305ST-17B">17b</A> Brumbaugh JS. Sen A. J. Am. Chem. Soc.  1988,  110:  803 

<A NAME="RU19305ST-18">18</A> Hirabayashi K. Mori A. Kawashima J. Suguro M. Nishihara Y. Hiyama T. J. Org. Chem.  2000,  65:  5342 

<A NAME="RU19305ST-19">19</A>

Typical Procedure for the Cross-Coupling Reactions of Acid Chlorides 1 with Boronic Acids 2.
To phenylboronic acid (1a, 244 mg, 2 mmol), CuTC (191 mg, 1 mmol), Pd(dba)₂ (29 mg, 0.05 mmol), and PPh₃ (26.2 mg, 0.1 mmol), were added dry Et₂O (30 mL) and benzoyl chloride (2a, 116 µL, 1 mmol) at r.t. The reddish brown suspension was stirred for 1 h at r.t. and monitored by GC and TLC. After completion of the reaction, the reaction mixture was passed briefly through a Celite pad. Further, the pad was washed with Et₂O (2 × 10 mL). The combined organics were concentrated with a rotary evaporator to give a viscous oil or solid. The residue was purified by flash column chromatography on silica gel (hexane-EtOAc = 9:1, R _f = 0.47), compound 3a (142 mg, 0.78 mmol, 78%) was obtained as a white solid. ¹H NMR (300 MHz, CDCl₃): δ = 7.46-7.51 (m, 4 H), 7.56-7.62 (m, 2 H), 7.79-7.83 (m, 4 H). ¹³C{¹H} NMR (75 MHz, CDCl₃): δ = 128.1, 129.9, 132.3, 137.4, 196.5.