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

Research output: Contribution to journalArticleResearchpeer-review

9 Citations (Scopus)

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.

Original languageEnglish
Article numberP04408SS
Pages (from-to)2764-2770
Number of pages7
JournalSynthesis
Issue number17
DOIs
Publication statusPublished - 2 Sep 2008
Externally publishedYes

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Aniline
Esters
Derivatives
Acids
palladium(II) acetate
3-anisidine

Cite this

Lorimer, Anna V. ; O'Connor, Patrick D. ; Brimble, Margaret A. / Buchwald-Hartwig Mono-N-arylation with 2,6-dihaloisonicotinic acid derivatives : A convenient desymmetrization method. In: Synthesis. 2008 ; No. 17. pp. 2764-2770.
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Buchwald-Hartwig Mono-N-arylation with 2,6-dihaloisonicotinic acid derivatives : A convenient desymmetrization method. / Lorimer, Anna V.; O'Connor, Patrick D.; Brimble, Margaret A.

In: Synthesis, No. 17, P04408SS, 02.09.2008, p. 2764-2770.

Research output: Contribution to journalArticleResearchpeer-review

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T1 - Buchwald-Hartwig Mono-N-arylation with 2,6-dihaloisonicotinic acid derivatives

T2 - A convenient desymmetrization method

AU - Lorimer, Anna V.

AU - O'Connor, Patrick D.

AU - Brimble, Margaret A.

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N2 - 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.

AB - 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.

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