Palladium-Catalyzed N-Arylation of Bis(ortho-substituted aryl)amines: an Efficient Method for Preparing Sterically Congested Triarylamines

Abstract

Bis(ortho-substituted aryl)amines were arylated on the nitrogen atom with various haloarenes in high yields using the palladium catalyst, which was generated from palladium(II) acetate and tri(tert-butyl)phosphine.

amination - arylation - cross-coupling - homogeneous catalysis - palladium

References and Notes

Representative reviews:

<A NAME="RU03710ST-1A">1a</A> Shirota Y. J. Mater. Chem.  2000,  10:  1 

<A NAME="RU03710ST-1B">1b</A> Shirota Y. J. Mater. Chem.  2005,  15:  75 

<A NAME="RU03710ST-1C">1c</A> Shirota Y. Kageyama H. Chem. Rev.  2007,  107:  953 

<A NAME="RU03710ST-1D">1d</A> Ning Z. Tian H. Chem. Commun.  2009,  5483 

Recent reviews:

<A NAME="RU03710ST-2A">2a</A> Shekhar S. Shen Q. Barrios-Landeros F. Hartwig JF. In The Chemistry of Anilines   Rappoport Z. Wiley Interscience; New York: 2007.  p.455 

<A NAME="RU03710ST-2B">2b</A> Surry DS. Buchwald SL. Angew. Chem. Int. Ed.  2008,  47:  6338 

<A NAME="RU03710ST-3A">3a</A> Liu Y.-H. Chen C. Yang L.-M. Tetrahedron Lett.  2006,  47:  9275 

<A NAME="RU03710ST-3B">3b</A> Nandurkar NS. Bhanushali MJ. Bhor MD. Bhanage BM. Tetrahedron Lett.  2007,  48:  6537 

<A NAME="RU03710ST-3C">3c</A> Xu H. Wolf C. Chem. Commun.  2009,  1715 

<A NAME="RU03710ST-4">4</A> Hartwig JF. Kawatsura M. Hauck SI. Shaughnessy KH. Alcazar-Roman LM. J. Org. Chem.  1999,  64:  5575 

<A NAME="RU03710ST-5A">5a</A> Kataoka N. Shelby Q. Stambuli JP. Hartwig JF.
J. Org. Chem.  2002,  67:  5553 

<A NAME="RU03710ST-5B">5b</A> Kuwano R. Utsunomiya M. Hartwig JF. J. Org. Chem.  2002,  67:  6479 

<A NAME="RU03710ST-5C">5c</A> Urgaonkar S. Xu J.-H. Verkade JG. J. Org. Chem.  2003,  68:  8416 

<A NAME="RU03710ST-5D">5d</A> Urgaonkar S. Verkade JG. J. Org. Chem.  2004,  69:  9135 

<A NAME="RU03710ST-5E">5e</A> Reddy CV. Kingston JV. Verkade JG. J. Org. Chem.  2008,  73:  3047 

<A NAME="RU03710ST-5F">5f</A> Hirai Y. Uozumi Y. Chem. Commun.  2010,  46:  1103 

<A NAME="RU03710ST-6A">6a</A> Chae HK. Eddaoudi M. Kim J. Hauck SI. Hartwig JF. O’Keeffe M. Yaghi OM. J. Am. Chem. Soc.  2001,  123:  11482 

<A NAME="RU03710ST-6B">6b</A> Jin Z. Lucht BL. J. Am. Chem. Soc.  2005,  127:  5586 

<A NAME="RU03710ST-6C">6c</A> Yan XZ. Pawlas J. Goodson T. Hartwig JF. J. Am. Chem. Soc.  2005,  127:  9105 

<A NAME="RU03710ST-6D">6d</A> Fukuzaki E. Nishide H. J. Am. Chem. Soc.  2006,  128:  996 

<A NAME="RU03710ST-7A">7a</A> Plater MJ. McKay M. Jackson T. J. Chem. Soc., Perkin Trans. 1  2000,  2695 

<A NAME="RU03710ST-7B">7b</A> Yano M. Furuya T. Yonezawa M. Tatsumi M. Oyama M. Sato K. Takui T. Polyhedron  2005,  24:  2121 

<A NAME="RU03710ST-7C">7c</A> Nishide Y. Osuga H. Iwata K. Tanaka K. Sakamoto H. Bull. Chem. Soc. Jpn.  2008,  81:  1322 

<A NAME="RU03710ST-8">8</A> Chen C.-T. Chiang C.-L. Lin Y.-C. Chan L.-H. Huang C.-H. Tsai Z.-W. Chen C.-T. Org. Lett.  2003,  5:  1261 

<A NAME="RU03710ST-9">9</A> Driver MS. Hartwig JF. J. Am. Chem. Soc.  1996,  118:  7217 

<A NAME="RU03710ST-10">10</A> Wolfe JP. Wagaw S. Buchwald SL. J. Am. Chem. Soc.  1996,  118:  7215 

<A NAME="RU03710ST-11">11</A> Urgaonkar S. Nagarajan M. Verkade JG. Org. Lett.  2003,  5:  815 

<A NAME="RU03710ST-12">12</A> Stauffer SR. Lee S. Stambuli JP. Hauck SI. Hartwig JF. Org. Lett.  2000,  2:  1423 

<A NAME="RU03710ST-13A">13a</A> Old DW. Wolfe JP. Buchwald SL. J. Am. Chem. Soc.  1998,  120:  9722 

<A NAME="RU03710ST-13B">13b</A> Wolfe JP. Buchwald SL. Angew. Chem. Int. Ed.  1999,  38:  2413 

<A NAME="RU03710ST-14">14</A> Suzuki K. Hori Y. Kobayashi T. Adv. Synth. Catal.  2008,  350:  652 

<A NAME="RU03710ST-15">15</A> Ehrentraut A. Zapf A. Beller M. J. Mol. Catal. A: Chem.  2002,  182-183:  515 

<A NAME="RU03710ST-16A">16a</A> Nishiyama M. Yamamoto T. Koie Y. Tetrahedron Lett.  1998,  39:  617 

<A NAME="RU03710ST-16B">16b</A> Yamamoto T. Nishiyama M. Koie Y. Tetrahedron Lett.  1998,  39:  2367 

<A NAME="RU03710ST-17">17</A>

Typical Procedure for the N-Arylation of Bis( ortho -substituted aryl)amines 2
Under a nitrogen atmosphere, a haloarene 1 or 4 (1.5 mmol) was added to a mixture of (t-Bu)₃P (4.1 mg, 20 µmol), Pd(OAc)₂ (2.2 mg, 10 µmol), NaOt-Bu (144 mg, 1.5 mmol), and a diarylamine 2 (1.0 mmol) in toluene (2.0 mL). The reaction mixture was stirred at 120 ˚C for 2-24 h, cooled to r.t., diluted with H₂O, and then extracted with EtOAc. The combined organic layer was washed with brine, dried over Na₂SO₄, and then evaporated under reduced pressure. The residue was purified with a flash column chromatography (EtOAc-hexane) to give the desired triarylamine 3.

<A NAME="RU03710ST-18">18</A> Stambuli JP. Bühl M. Hartwig JF. J. Am. Chem. Soc.  2002,  124:  9346 

<A NAME="RU03710ST-19A">19a</A> Mann G. Hartwig JF. J. Am. Chem. Soc.  1996,  118:  13109 

<A NAME="RU03710ST-19B">19b</A> Driver MS. Hartwig JF. Organometallics  1997,  16:  5706 

<A NAME="RU03710ST-20">20</A> Yamashita M. Hartwig JF. J. Am. Chem. Soc.  2004,  126:  5344 

<A NAME="RU03710ST-21">21</A> Alcazar-Roman LM. Hartwig JF. J. Am. Chem. Soc.  2001,  123:  12905 

<A NAME="RU03710ST-22">22</A>

The competitive experiment using an equimolar mixture of 1g and 1i afforded 3g and 3i by a ratio of 48:52. See details in the Supporting Information.

<A NAME="RU03710ST-23">23</A>

The competitive experiment using an equimolar mixture of 2a and 2c afforded 3a and 3k by a ratio of 32:68. See details in the Supporting Information.

<A NAME="RU03710ST-24">24</A> Yamashita M. Vicario JVC. Hartwig JF. J. Am. Chem. Soc.  2003,  125:  16347