Synthesis of Tetra-ortho-Substituted Biaryls Using Aryltriolborates

Abstract

Tetra-ortho-substituted biaryls were synthesized by cross-coupling between 2,6-disubstituted bromoarenes and aryltriolborates possessing substituents at ortho carbon. The use of a copper(I) halide such as CuCl (20 mol%) with a palladium catalyst was found to be highly effective to give such sterically hindered biaryls in good yields.

cross-coupling - palladium catalyst - aryltriolborates - tetra-ortho-substituted biaryls

References and Notes

For reviews, see:

<A NAME="RU03311ST-1A">1a</A> Miyaura N. Suzuki A. Chem. Rev.  1995,  95:  2457 

<A NAME="RU03311ST-1B">1b</A> Suzuki A. In Metal-Catalyzed Cross-Coupling Reactions   Diederich F. Stang PJ. Wiley-VCH; Weinheim: 1998.  p.49-98  

<A NAME="RU03311ST-1C">1c</A> Miyaura N. In Advances in Metal-Organic Chemistry   Vol. 6:  Liebeskind LS. JAI Press; Stamford: 1998.  p.187 

<A NAME="RU03311ST-1D">1d</A> Miyaura N. In Topics in Current Chemistry   Vol. 219:  Springer; Berlin: 2002.  p.11 

<A NAME="RU03311ST-1E">1e</A> Suzuki A. Brown HC. Suzuki Coupling, In Organic Synthesis via Boranes   Vol. 3:  Aldrich Chemical Co.; Milwaukee: 2003. 

<A NAME="RU03311ST-1F">1f</A> Miyaura N. In Metal-Catalyzed Cross-Coupling Reactions   2nd ed.:  de Meijere A. Diederich F. Wiley-VCH; Weinheim: 2005.  p.41-124  

<A NAME="RU03311ST-2A">2a</A> Hassan J. Svignon M. Gozzi C. Schulz E. Lemaire M. Chem. Rev.  2002,  102:  1359 

<A NAME="RU03311ST-2B">2b</A> Bringmann G. Gulder T. Gulder TAM. Breuning M. Chem. Rev.  2011,  111:  563 

<A NAME="RU03311ST-3A">3a</A> Upender V. Pollart DJ. Liu J. Hobbs PD. Olsen C. Chao W.-R. Bowden B. Crase JL. Thomas DW. Pandey A. Lawson JA. Dawson MI. J. Heterocycl. Chem.  1996,  33:  1371 

<A NAME="RU03311ST-3B">3b</A> Hoye TR. Chen M. J. Org. Chem.  1996,  61:  7940 

<A NAME="RU03311ST-3C">3c</A> Monovich LG. Huérou YL. Rönn M. Molander GA. J. Am. Chem. Soc.  2000,  122:  52 

<A NAME="RU03311ST-4A">4a</A> Dai C. Fu GC. J. Am. Chem. Soc.  2001,  123:  2719 

<A NAME="RU03311ST-4B">4b</A> Littke AF. Schwarz L. Fu GC. J. Am. Chem. Soc.  2002,  124:  6343 

<A NAME="RU03311ST-5A">5a</A> Yin J. Rainka MP. Zhang XX. Buchwald SL.
J. Am. Chem. Soc.  2002,  124:  1162 

<A NAME="RU03311ST-5B">5b</A> Walker SD. Barder TE. Martinelli JR. Buchwald SL. Angew. Chem. Int. Ed.  2004,  43:  1871 

<A NAME="RU03311ST-5C">5c</A> Milne JE. Buchwald SL. J. Am. Chem. Soc.  2004,  126:  13028 

<A NAME="RU03311ST-5D">5d</A> Barder TE. Walker SD. Martinelli JR. Buchwald SL. J. Am. Chem. Soc.  2005,  127:  4685 

<A NAME="RU03311ST-6A">6a</A> Hoshi T. Nakazawa T. Saitoh I. Mori A. Suzuki T. Sakai J. Hagiwara H. Org. Lett.  2008,  10:  2063 

<A NAME="RU03311ST-6B">6b</A> Hoshi T. Saitoh I. Nakazawa T. Suzuki T. Sakai J. Hagiwara H. J. Org. Chem.  2009,  74:  4013 

<A NAME="RU03311ST-7">7</A> Tang W. Capacci AD. Wei X. Ki W. White A. Patel ND. Savoie J. Gao JJ. Rodriguez S. Qu B. Haddad N. Lu BZ. Krishnamurthy D. Yee NK. Senanayake CH. Angew. Chem. Int. Ed.  2010,  49:  5879 

<A NAME="RU03311ST-8">8</A> So CM. Chow WK. Choy PY. Lau CP. Kwong FY. Chem. Eur. J.  2010,  16:  7996 

<A NAME="RU03311ST-9">9</A> To SC. Kwong FY. Chem. Commun.  2011,  47:  5079 

<A NAME="RU03311ST-10">10</A> Altenhoff G. Goddard R. Lehmann CW. Glorius F.
J. Am. Chem. Soc.  2004,  126:  15195 

<A NAME="RU03311ST-11">11</A> Song C. Ma Y. Chai Q. Ma C. Jiang W. Adrus MB. Tetrahedron  2005,  61:  7438 

<A NAME="RU03311ST-12">12</A> Organ MG. Çalimsiz S. Sayah M. Hoi KH. Lough AJ. Angew. Chem. Int. Ed.  2009,  48:  2383 

<A NAME="RU03311ST-13">13</A> Ackermann L. Potukuchi HK. Althammer A. Borm R. Mayer P. Org. Lett.  2010,  12:  1004 

<A NAME="RU03311ST-14">14</A> Lee D.-H. Jin M.-J. Org. Lett.  2011,  13:  252 

<A NAME="RU03311ST-15A">15a</A> Yamamoto Y. Takizawa M. Yu X.-Q. Miyaura N. Angew. Chem. Int. Ed.  2008,  47:  928 

<A NAME="RU03311ST-15B">15b</A> Yamamoto Y. Takizawa M. Yu X.-Q. Miyaura N. Heterocycles  2010,  80:  359 

<A NAME="RU03311ST-15C">15c</A> Yamamoto Y. Sugai J. Takizawa M. Miyaura N. Org. Synth.  2011,  88:  79 

<A NAME="RU03311ST-16">16</A> Yu X.-Q. Yamamoto Y. Miyaura N. Chem. Asian J.  2008,  3:  1517 

<A NAME="RU03311ST-17A">17a</A> Yu X.-Q. Yamamoto Y. Miyaura N. Synlett  2009,  994 

<A NAME="RU03311ST-17B">17b</A> Yu X.-Q. Shirai T. Yamamoto Y. Miyaura N. Chem. Asian J.  2011,  6:  932 

<A NAME="RU03311ST-18A">18a</A> Kuvila HG. Reuwer JF. Mangravite JA. J. Am. Chem. Soc.  1964,  86:  2666 

<A NAME="RU03311ST-18B">18b</A> Brown RD. Buchanan AS. Humffray AA. Aust. J. Chem.  1965,  18:  1521 

<A NAME="RU03311ST-19A">19a</A> Tyrrell E. Brookes P. Synthesis  2003,  469 

<A NAME="RU03311ST-19B">19b</A> Molander GA. Biolato B. J. Org. Chem.  2003,  68:  4302 

<A NAME="RU03311ST-19C">19c</A> Campeau L.-C. Fagnou K. Chem. Soc. Rev.  2007,  36:  1058 

<A NAME="RU03311ST-20A">20a</A> Hodgson PB. Salingue FH. Tetrahedron Lett.  2004,  45:  685 

<A NAME="RU03311ST-20B">20b</A> Gros P. Doudouh A. Fort Y. Tetrahedron Lett.  2004,  45:  6239 

<A NAME="RU03311ST-20C">20c</A> Jones NA. Antoon JW. Browie AL. Borak JB. Stevens EP. J. Heterocycl. Chem.  2007,  44:  363 

<A NAME="RU03311ST-20D">20d</A> Gütz C. Lützen A. Synthesis  2010,  85 

<A NAME="RU03311ST-21">21</A> Deng JZ. Paone DV. Ginnetti AT. Kurihara H. Dreher SD. Weissman SA. Stauffer SR. Burgey CS. Org. Lett.  2009,  11:  345 

<A NAME="RU03311ST-22">22</A>

General Procedure for the Synthesis of ortho -Substituted Biaryls
The aryl bromide (0.5 mmol), aryl triolborate (0.75 mmol), Pd(OAc)₂ (5 mol%), BIPHEP (5.5 mol%), and CuCl (0.1 mmol) were placed in a flash under nitrogen atmosphere. Anhyd DMF (5 mL) was added. The mixture was stirred at 80 ˚C for 14 h. After cooling to r.t., the crude mixture was filtered through a plug of Celite and washed with Et₂O. The filtrate was then concentrated in vacuo to afford the crude product, which was further purified by chromatography on silica gel with hexanes-EtOAc (99:1 to 10:1).

<A NAME="RU03311ST-23">23</A> Tyrrell E. Brookes P. Synthesis  2003,  469