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      Palladium-Catalyzed Amination of Aryl Chlorides and Bromides with Ammonium Salts

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      Publication date (Electronic):
      Journal: Organic Letters
      Publisher: American Chemical Society

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          Abstract

          We report the palladium-catalyzed coupling of aryl halides with ammonia and gaseous amines as their ammonium salts. The coupling of aryl chlorides and ortho-substituted aryl bromides with ammonium sulfate forms anilines with higher selectivity for the primary arylamine over the diarylamine than couplings with ammonia in dioxane. The resting state for the reactions of aryl chlorides is different from the resting state for the reactions of aryl bromides, and this change in resting states is proposed to account for a difference in selectivities for reactions of the two haloarenes.

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          A multiligand based Pd catalyst for C-N cross-coupling reactions.

          Brett Fors, Stephen Buchwald (2010)
          An alternative approach to catalyst development, which led to a Pd catalyst based on two biarylphosphine ligands for C-N cross-coupling reactions, is reported. By effectively being able to take the form of multiple catalysts this system manifests the best properties that catalysts based on either of the two ligands exhibit separately and displays the highest reactivity and substrate scope of any system that has been reported to date for these reactions.
          Article 0 comments Cited 51 times – based on 0 reviews     Review now
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            Palladium-catalyzed coupling of ammonia with aryl chlorides, bromides, iodides, and sulfonates: a general method for the preparation of primary arylamines.

            Giang D Vo, John Hartwig (2009)
            We report that the complex generated from Pd[P(o-tol)(3)](2) and the alkylbisphosphine CyPF-t-Bu is a highly active and selective catalyst for the coupling of ammonia with aryl chlorides, bromides, iodides, and sulfonates. The couplings of ammonia with this catalyst conducted with a solution of ammonia in dioxane form primary arylamines from a variety of aryl electrophiles in high yields. Catalyst loadings as low as 0.1 mol % were sufficient for reactions of many aryl chlorides and bromides. In the presence of this catalyst, aryl sulfonates also coupled with ammonia for the first time in high yields. A comparison of reactions in the presence of this catalyst versus those in the presence of existing copper and palladium systems revealed a complementary, if not broader, substrate scope. The utility of this method to generate amides, imides, and carbamates is illustrated by a one-pot synthesis of a small library of these carbonyl compounds from aryl bromides and chlorides, ammonia, and acid chlorides or anhydrides. Mechanistic studies show that reactions conducted with the combination of Pd[P(o-tol)(3)](2) and CyPF-t-Bu as catalyst occur with faster rates and higher yields than those conducted with CyPF-t-Bu and palladiun(II) as catalyst precursors because of the low concentration of active catalyst that is generated from the combination of palladium(II), ammonia, and base.
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              Resting state and elementary steps of the coupling of aryl halides with thiols catalyzed by alkylbisphosphine complexes of palladium.

              Elsa Alvaro, John Hartwig (2009)
              Detailed mechanistic studies on the coupling of aryl halides with thiols catalyzed by palladium complexes of the alkylbisphosphine ligand CyPF-(t)Bu (1-dicyclohexylphosphino-2-di-tert-butylphosphinoethylferrocene) are reported. The elementary steps that constitute the catalytic cycle, i.e. oxidative addition, transmetalation and reductive elimination, have been studied, and their relative rates are reported. Each of the steps of the catalytic process occurs at temperatures that are much lower than those required for the reactions catalyzed by a combination of palladium precursors and CyPF-(t)Bu. To explain these differences in rates between the catalytic and stoichiometric reactions, studies were conducted to identify the resting state of the catalyst of the reactions catalyzed by a combination of Pd(OAc)(2) and CyPF-(t)Bu, a combination of Pd(dba)(2) and CyPF-(t)Bu, or the likely intermediate Pd(CyPF-(t)Bu)(Ar)(Br). These data show that the major palladium complex in each case lies off of the catalytic cycle. The resting state of the reactions catalyzed by Pd(OAc)(2) and CyPF-(t)Bu was the palladium bis-thiolate complex [Pd(CyPF-(t)Bu)(SR)(2)] (R = alkyl or aryl). The resting state in reactions catalyzed by Pd(2)(dba)(3) and CyPF-(t)Bu was the binuclear complex [Pd(CyPF-(t)Bu)](2)(mu(2),eta(2)-dba) (9). The resting states of reactions of both aromatic and aliphatic thiols catalyzed by [Pd(CyPF-(t)Bu)(p-tolyl)(Br)] (3a) were the hydridopalladium thiolate complexes [Pd(CyPF-(t)Bu)(H)(SR)] (R= alkyl and aryl). All these palladium species have been prepared independently, and the mechanisms by which they enter the catalytic cycle have been examined in detail. These features of the reaction catalyzed by palladium and CyPF-(t)Bu have been compared with those of reactions catalyzed by the alkylbisphosphine DiPPF and Pd(OAc)(2) or Pd(dba)(2). Our data indicate that the resting states of these reactions are similar to each other and that our mechanistic conclusions about reactions catalyzed by palladium and CyPF-(t)Bu can be extrapolated to reactions catalyzed by complexes of other electron-rich bisphosphines.
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                Author and article information

                Journal
                Journal ID (nlm-ta): Org Lett
                Journal ID (iso-abbrev): Org. Lett
                Journal ID (publisher-id): ol
                Journal ID (coden): orlef7
                Title: Organic Letters
                Publisher: American Chemical Society
                ISSN (Print): 1523-7060
                ISSN (Electronic): 1523-7052
                Publication date (Electronic): 18 August 2014
                Publication date (Print): 05 September 2014
                Volume: 16
                Issue: 17
                Pages: 4388-4391
                Affiliations
                [1]Department of Chemistry, University of California , Berkeley, California 94720, United States
                Author notes
                Article
                DOI: 10.1021/ol501739g
                PMC ID: 4260968
                PubMed ID: 25133675
                SO-VID: 94ebc20d-41f5-4abb-88bf-484fb82a7778
                Copyright © Copyright © 2014 American Chemical Society
                License:

                This is an open access article published under an ACS AuthorChoice License, which permits copying and redistribution of the article or any adaptations for non-commercial purposes.

                History
                Date received : 16 June 2014
                Categories
                Subject: Letter
                Custom metadata
                document-id-old-9 ol501739g
                document-id-new-14 ol-2014-01739g
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                ScienceOpen disciplines: Organic & Biomolecular chemistry
                Data availability:
                ScienceOpen disciplines: Organic & Biomolecular chemistry

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