Buchwald-Hartwig Mono-N-arylation
with 2,6-Dihaloisonicotinic Acid Derivatives: A Convenient
Desymmetrization Method

Anna V. Lorimer; Patrick D. O’Connor; Margaret A. Brimble

doi:10.1055/s-2008-1067208

PAPER

Buchwald-Hartwig Mono-N-arylation with 2,6-Dihaloisonicotinic Acid Derivatives: A Convenient Desymmetrization Method

Anna V. Lorimer, Patrick D. O’Connor, Margaret A. Brimble*
Department of Chemistry, University of Auckland, 23 Symonds St., Auckland 1142, New Zealand
Fax: +64(9)3737422; e-Mail: m.brimble@auckland.ac.nz;

Abstract

Alle Artikel dieser Rubrik

Abstract

A method for the Buchwald-Hartwig mono-N-arylation of aniline with methyl 2,6-dichloroisonicotinate using Pd(OAc)₂, XPhos, and t-BuONa is reported. Use of m-anisidine under the same conditions resulted in the amidation of the methyl ester. Mono-N-arylation of m-anisidine with 2,6-dichloro-N,N-diisopropylisonicotinamide and 2,6-dibromo-N,N-diisopropylisonicotinamide, however, was successfully achieved using Pd(OAc)₂/XPhos/t-BuONa or Pd(OAc)₂/(±)-BINAP/K₂CO₃, respectively. The present study demonstrates the sensitivity of this cross-coupling method to both the steric and electronic nature of the coupling partners.

Key words

Buchwald-Hartwig N-arylation - Pd(0) cross-coupling - 2,6-dihaloisonicotinates

Volltext

Referenzen

References

1 Janey JM. Buchwald-Hartwig Amination, In Name Reactions for Functional Group Transformations Li JJ. Wiley; Hoboken NJ: 2007. p.566-611

2 Schlummer B. Scholz U. Adv. Synth. Catal. 2004, 346: 1599

3 Buchwald SL. Mauger C. Mignani G. Scholz U. Adv. Synth. Catal. 2006, 348: 23

4a Wagaw S. Buchwald SL. J. Org. Chem. 1996, 61: 7240

4b Li JJ. Wang Z. Mitchell LH. J. Org. Chem. 2007, 72: 3606

5a Barun O. Patra PK. Junjappa H. Tetrahedron Lett. 1999, 40: 3797

5b Molina P. Freneda PM. Sanz MA. Foces-Foces C. Arellano MCRD. Tetrahedron 1998, 54: 9623 ; and references cited therein

6 Maes BUW. Loones KTJ. Hostyn S. Diels G. Rombouts G. Tetrahedron 2004, 60: 11559

7 Maes BUW. Loones KTJ. Lemiere GLF. Domisse RA. Synlett 2003, 1822

8 Kim J. Shin-ya K. Furihata K. Hayakawa Y. Seto H. Tetrahedron Lett. 1997, 38: 3431

9 Amb CM. Rasmussen SC. J. Org. Chem. 2006, 71: 4696

10 Kelly TR. Lee Y.-J. Mears RJ. J. Org. Chem. 1997, 62: 2774

11 Wolfe JP. Tomori H. Sadighi JP. Yin J. Buchwald SL. J. Org. Chem. 2000, 65: 1158

12 Yang BH. Buchwald SL. J. Organomet. Chem. 1999, 576: 125

13 Wolfe JP. Wagaw S. Marcoux J.-F. Buchwald SL. Acc. Chem. Res. 1998, 31: 805

14 Jonckers THM. Maes BUW. Lemiere F. Dommisse R. Tetrahedron 2001, 57: 7027

15 Mello JV. Finney NS. Org. Lett. 2001, 3: 4263