Solvent-free Zn (NSNO) complex-catalysed dihydroboration of nitriles

Ataie, Saeed; Ovens, Jeffrey S.; Baker, R. Tom

doi:10.1039/d2cc03517k

Cited by 13 publications

(12 citation statements)

References 34 publications

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“…15,16 We have recently been comparing 'soft' thiolate-(L 1 ) and 'hard' amido-(L 2 ) SNS ligands (Schemes 2 and 3) in ligandassisted catalysis. 17,18 Working with base metals from Mn to Zn we demonstrated several different bifunctional mechanisms for catalysed hydroboration [19][20][21][22][23] and hydrosilylation 24 of carbonyls, nitriles 25,26 and N-heterocycles. 27 In expanding the catalytic applications of these coordination complexes, we sought to use these ligands to stabilize Cu(I) and evaluate their activity in CuAAC.…”

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confidence: 99%

Tetracopper(i) thiolate- and amido-(SNS) complexes and copper-catalyzed azide–alkyne cycloaddition in water

Khanzadeh,

Ataie,

Baker

2023

Dalton Trans.

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confidence: 99%

Tetracopper(i) thiolate- and amido-(SNS) complexes and copper-catalyzed azide–alkyne cycloaddition in water

Khanzadeh,

Ataie,

Baker

2023

Dalton Trans.

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“…Based on stoichiometric experiments, isolation of intermediate, and previous literature reports, − the most plausible mechanism for the zinc hydride-catalyzed hydroboration of nitriles is shown in Scheme .…”

Section: Resultsmentioning

confidence: 99%

Zinc Hydride-Catalyzed Dihydroboration of Isonitriles and Nitriles: Mechanistic Studies with the Structurally Characterized Zinc Intermediates

et al. 2023

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The conjugated bis-guanidinate (CBG)-stabilized zinc hydride, [{LZnH} 2 ; (L = {(ArNH)(ArN)−C�N− C�(NAr)(NHAr)}; Ar = 2,6-Et 2 -C 6 H 3 )] (Zn-1), is shown to be a highly active catalyst for the double reduction of isonitriles and nitriles with pinacolborane (HBpin) in this study. A wide array of isonitriles and nitriles, including aryl and alkyl groups, underwent hydroboration to afford exclusively 1,2-and 1,1-diborylated amine products, respectively. A series of stoichiometric reactions were performed to understand the reaction mechanisms. Hydroboration of isonitrile proceeds through the formation of zinc formimidoyl complex, [LZnC(H)N( t Bu)] 2 (Zn-2), while nitrile hydroboration through zinc vinylidenamido complex, [LZnNC(H)(C 6 H 5 )] 2 (Zn-3). Moreover, compounds Zn-2 and Zn-3 are isolated and thoroughly characterized. Such molecular zinc complexes are rare in the literature.

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“…The synthesis of zinc complexes has experienced remarkable renewal and rapid expansion during the last 20 years. [1][2][3][4][5][6][7][8][9][10][11][12] The motivations of many scientists for the preparation of various zinc complexes have been driven by the extensive applications of these complexes as catalysts for a series of organic reactions. These reactions include hydro-alkoxylation cyclization of alkynyl alcohols, [13] hydroamination of alkenes, [14] CO 2 /epoxide copolymerization, [15] carboxylic acid ester hydrolysis, [16] asymmetric Michael addition to nitroalkenes, [17] ring-opening polymerization of cyclic esters, [18] and so forth.…”

Section: Introductionmentioning

confidence: 99%

Synthesis and Characterization of Zinc, Lithium and Magnesium Complexes Containing Pyrrolyl Ligands, and Utilization as Catalysts in Borylation of Aryl Iodides and Hydroboration of Aldehydes and Ketones

Dang¹,

Jia²,

Wang³

et al. 2023

Chinese Journal of Organic Chemistry

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The reactions of ZnEt2 with two pyrrolyl ligands 2-(2-((((1H-pyrrol-2-yl)methylene)amino)methyl)-1H-pyrrol-1yl)-N,N-dimethylethan-1-amine (HL1) and N-((1H-pyrrol-2-yl)methyl)-1-(1H-pyrrol-2-yl)methanimine (H2L2) generated a zinc ethyl compound [Zn(L1)Et] (1) and a dinuclear complex [Zn2(L2)2(THF)2] (2). The complexes were characterized by 1 H NMR, 13 C NMR, elemental analysis, and single-crystal X-ray diffraction. Complexes 1 and 2 were employed as catalysts for the borylation of aryl iodides with B2Pin2 (B2Pin2＝4,4,4',4',5,5,5',5'-octamethyl-2,2'-bis(1,3,2-dioxaborolane)). They were both active for this coupling reaction. Complex 1 displays higher activity than that of 2. This borylation transformation promoted by 1 features mild condition, wide substrate scope and high functional group compatibility. Moreover, the catalytic activities of two known compounds previously reported by our group, namely, [Li2(L1)2] (3) and [Mg(L1)2(THF)2] (4), toward borylation of aryl iodides with B2Pin2 were also explored. They cannot catalyze this coupling reaction. Nevertheless, complexes 3 and 4 were catalytically active toward hydroboration of aldehydes and ketones by pinacolborane (HBpin), giving a variety of borate esters in excellent yields in a very short time.

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Solvent-free Zn (NSNO) complex-catalysed dihydroboration of nitriles

Abstract: A zinc complex uses its aryloxide (vs. amido) donor to generate a Zn–H catalyst that effects quantitative, solvent-free hydroboration of nitriles to the corresponding diborylamines at 1 mol% catalyst loading.

Cited by 13 publications

References 34 publications

Tetracopper(i) thiolate- and amido-(SNS) complexes and copper-catalyzed azide–alkyne cycloaddition in water

Tetracopper(i) thiolate- and amido-(SNS) complexes and copper-catalyzed azide–alkyne cycloaddition in water

Zinc Hydride-Catalyzed Dihydroboration of Isonitriles and Nitriles: Mechanistic Studies with the Structurally Characterized Zinc Intermediates

Synthesis and Characterization of Zinc, Lithium and Magnesium Complexes Containing Pyrrolyl Ligands, and Utilization as Catalysts in Borylation of Aryl Iodides and Hydroboration of Aldehydes and Ketones

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