First Intramolecular Alkylation of Nitriles with Primary and Secondary Alcohols Catalyzed by Iridium Complexes

Anxionnat, Bruno; Pardo, Domingo Gomez; Ricci, Gino; Cossy, Janine

doi:10.1002/ejoc.201200850

Cited by 34 publications

(16 citation statements)

References 31 publications

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“…Thereaction of 35 and 36 affords the hydroxy amide 37 which can be further converted into ac yclic imide by dehydrogenative formation of the hemiaminal 38 as apotential intermediate. [26] Vogt et al reported ruthenium catalyst systems,c omprising [Ru 3 (CO) 12 ]and CataCXiumPCy (40), for intramolecular cyclization of a,w-amino alcohols to afford the cyclic amines 41 as well as the cyclic amides 42 [Eq. (13)].…”

Section: Angewandte Minireviewsmentioning

confidence: 99%

“…(24)]. [40] Iridium catalytic systems such as [{Cp*IrCl 2 } 2 ]a nd [{Ir(cod)Cl} 2 ]/PPh 3 were highly efficient catalysts under microwave conditions.Both catalytic systems showed similar reactivities and cis/trans selectivities for the construction of chromanes,w hereas [{Ir(cod)Cl} 2 ]/PPh 3 showed better yields for the synthesis of thiochromane-4-carbonitrile.T he reaction path consists of initial catalytic dehydrogenation of an alcohol to form acarbonyl compound and subsequent intramolecular condensation of the carbonyl with an active methylene group to provide olefin functionalities.F inally hydrogenation of the condensed product utilizing the borrowed hydrogen affords the corresponding O-and S-containing heterocyclic compounds 85.…”

Section: Angewandte Minireviewsmentioning

confidence: 99%

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Transition‐Metal‐Catalyzed Hydrogen‐Transfer Annulations: Access to Heterocyclic Scaffolds

et al. 2015

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The ability of hydrogen-transfer transition-metal catalysts, which enable increasingly rapid access to important structural scaffolds from simple starting materials, has led to a plethora of research efforts on the construction of heterocyclic scaffolds. Transition-metal-catalyzed hydrogen-transfer annulations are environmentally benign and highly atom-economical as they release of water and hydrogen as by-product and utilize renewable feedstock alcohols as starting materials. Recent advances in this field with respect to the annulations of alcohols with various nucleophilic partners, thus leading to the formation of heterocyclic scaffolds, are highlighted herein.

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Section: Angewandte Minireviewsmentioning

confidence: 99%

Section: Angewandte Minireviewsmentioning

confidence: 99%

Transition‐Metal‐Catalyzed Hydrogen‐Transfer Annulations: Access to Heterocyclic Scaffolds

et al. 2015

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“…Since 1981, when Grigg and co‐workers first used RuH 2 (PPh 3 ) 4 as a catalyst in the alkylation of nitriles with alcohol, a lot of effort has been devoted to exploring various catalysts, including Ru, Rh, Ir, Pd, Os, Fe, and Mn. Of these, Ru complexes are the most reported, for example Gunanathan's group reported that Ru(PNP) (PNP = bis(2‐(diphenylphosphino)‐ethyl)amine) pincer complex showed good activity for α ‐alkylated reaction of arylmethyl nitriles .…”

Section: Introductionmentioning

confidence: 99%

“…[4] Later, alkylation of nitriles via borrowing hydrogen strategy with alcohol as alkylation agent, has been developed as one of the most attractive and atom-economic transformation, with only water as a byproduct. [5,6] Since 1981, when Grigg and co-workers first used RuH 2 (PPh 3 ) 4 as a catalyst in the alkylation of nitriles with alcohol, [7] a lot of effort has been devoted to exploring various catalysts, including Ru, [8][9][10][11][12][13][14][15] Rh, [16,17] Ir, [18][19][20][21][22] Pd, [23] Os, [24] Fe, [25] and Mn [26] . Of these, Ru complexes are the most reported, for example Gunanathan's group reported that Ru(PNP) (PNP = bis(2-(diphenylphosphino)-ethyl)amine) pincer complex showed good activity for α-alkylated reaction of arylmethyl nitriles.…”

Section: Introductionmentioning

confidence: 99%

Ru(II)‐^PBTNN^XN complex bearing functional 2‐(pyridin‐2‐yl)benzo[d]thiazole ligand catalyzed α‐alkylation of nitriles with alcohols

Huang

Hong

Sun

et al. 2020

Applied Organom Chemis

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Six tridentate NNN ligand precursors derived from 2‐(pyridin‐2‐yl)benzo[d]thiazole(PBT) with different linkers, PBTNNXN (X = NH, NMe, O, S) (1a–1f), have been successfully prepared. The electronic properties of PBTNNXN ligands are well tunable by differing linkers between PBT skeleton and the pyridine ring, and/or by introducing electron‐donating/withdrawing groups on the pyridine ring (R = OMe or F). The ligand precursors and representative complexes Ru (PBTNNNHN)Cl2(PPh3) (2a), Ru (PBTNNNMeN)Cl2(PPh3) (2b), and Ru (PBTNNSN)Cl2(PPh3) (2f) have been characterized by NMR spectroscopy, high‐resolution mass spectroscopy, and Fourier transform infrared (FT‐IR). The molecular structures of 1f, 2a, and 2f have been determined by X‐ray diffraction study. The results indicate that PBTNNNHN ligand in the complex presented coplanar with two five‐membered chelating rings. It should be noted that 2a featuring a NH group exhibits superior performance compared to those with other linkers (such as NMe, O, or S). A variety of heterocyclic and aromatic nitriles with aromatic and aliphatic alcohols have been explored in α‐alkylation for good to excellent yields. Based on kinetic experiments and mechanistic studies, a proposed mechanism was put forward. Ru‐H species and benzaldehyde, which was oxidized from benzyl alcohol, were detected in the catalytic cycle.

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“…In the Supporting Information of the original article, 1 spectra for 1 , 3 , trans‐ 4 , cis‐ 4 ′, 5a , 5c , 7 , 10 , 11 , 12 , 13 , 15 and trans‐ 16 were found to have been edited to remove solvents and impurities. Original products were located and the spectra were recorded and have been replaced for 1 , 5a , 5c , 7 , 10 , 11 and 15 .…”

mentioning

confidence: 99%