This study represents the first example an environmentally benign, sustainable, and practical synthesis of substituted quinolines and pyrimidines using combinations of 2-aminobenzyl alcohols and alcohols as well as benzamidine and two different alcohols, respectively. These reactions proceed with high atom efficiency via a sequence of dehydrogenation and condensation steps that give rise to selective C-C and C-N bond formations, thereby releasing 2 equiv of hydrogen and water. A hydride Mn(I) PNP pincer complex recently developed in our laboratory catalyzes this process in a very efficient way. A total of 15 different quinolines and 14 different pyrimidines were synthesized in isolated yields of up to 91 and 90%, respectively.
Herein, we describe an efficient coupling of alcohols and amines catalyzed by well-defined isoelectronic hydride Mn(I) and Fe(II) complexes, which are stabilized by a PNP ligand based on the 2,6-diaminopyridine scaffold. This reaction is an environmentally benign process implementing inexpensive, earth-abundant non-precious metal catalysts, and is based on the acceptorless alcohol dehydrogenation concept. A range of alcohols and amines including both aromatic and aliphatic substrates were efficiently converted in good to excellent isolated yields. Although in the case of Mn selectively imines were obtained, with Fe-exclusively monoalkylated amines were formed. These reactions proceed under base-free conditions and required the addition of molecular sieves.
Efficient alkylations of amines by alcohols catalyzed by well-defined Co(II) complexes are described that are stabilized by a PCP ligand (N,N'-bis(diisopropylphosphino)-N,N'-dimethyl-1,3-diaminobenzene) based on the 1,3-diaminobenzene scaffold. This reaction is an environmentally benign process implementing inexpensive, earth-abundant nonprecious metal catalysts and is based on the acceptorless alcohol dehydrogenation concept. A range of primary alcohols and aromatic amines were efficiently converted into mono-N-alkylated amines in good to excellent isolated yields.
As eries of well-defined iron(II)c omplexes of the types[ Fe(PNP)Br 2 ]a nd [Fe(PNP)(CO)Br 2 ] with PNP pincerl igands based on triazine andp yridine backbones were prepared and fully characterized. Thesec omplexes were tested as catalysts for the alkylation of amines by alcohols.T he high-spin complexes [Fe(PNP)Br 2 ]a re catalytically inactive. Thel ow-spin complexes [Fe(PNP)(CO)Br 2 ]b earing ac arbonyl co-ligand efficiently ands electively convert primary alcohols and aromatica nd benzylic amines selectively into mono-N-alkylateda mines in good to excellent isolated yields.Amechanisticp roposal is given. Scheme 2. Proposal for the formationo fc atalyst B (R = i-Pr). Scheme 3. Te ntative catalytic cycle with B as catalyst (R = i-Pr).
This study represents the first example of a manganese-catalyzed environmentally benign, practical three-component aminomethylation of activated aromatic compounds including naphtols, phenols, pyridines, indoles, carbazoles, and thiophenes in combination with amines and MeOH as a C1 source. These reactions proceed with high atom efficiency via a sequence of dehydrogenation and condensation steps which give rise to selective C-C and C-N bond formations, thereby releasing hydrogen and water. A well-defined hydride Mn(I) PNP pincer complex, recently developed in our laboratory, catalyzes this process in a very efficient way, and a total of 28 different aminomethylated products were synthesized and isolated yields of up to 91%. In a preliminary study, a related Fe(II) PNP pincer complex was shown to catalyze the methylation of 2-naphtol rather than its aminomethylation displaying again the divergent behavior of isoelectronic Mn(I) and Fe(II) PNP pincer systems.
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