A new and effective method for providing optically active monosubstituted malononitriles: selective reduction of α,β-unsaturated dinitriles catalyzed by copper hydride complexes

Copper(I) complexes of a new participative triphosphane ligand (2H) have been prepared and structurally characterized, in particular [Cu(2H)I] and [Cu(2)]2. Hydrogenation of the latter species afforded the trimetallic hydride species [Cu3(2)2(µ-H)] or in the presence of BEt3, [Cu(2H)(HBEt3)]. Their formation evidences transient formation of [Cu(2H)H] formed by hydrogenolysis of the Cu‒ N bond of [Cu(2)]2. [Cu(2H)(HBEt3)] behaves like a hydride complex and inserts CO2 to yield the formate product [Cu(2H)(O2CH)].

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Multinuclear Copper Hydride Complexes Supported by Polyphosphine Ligands

European Journal of Inorganic Chemistry ◽

10.1002/ejic.202000328 ◽

2020 ◽

Vol 2020 (23) ◽

pp. 2211-2226 ◽

Cited By ~ 3

Author(s):

Takayuki Nakajima ◽

Kanako Nakamae ◽

Yasuyuki Ura ◽

Tomoaki Tanase

Keyword(s):

Copper Hydride ◽

Hydride Complexes

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Using Alcohols As Simple H2-Equivalents for Copper-Catalysed Transfer Hydrogenations

10.26434/chemrxiv.9731279 ◽

2019 ◽

Author(s):

Trinadh Kaicharla ◽

Birte Zimmermann ◽

Martin Oestreich ◽

Johannes F. Teichert

Keyword(s):

Functional Groups ◽

Selective Reduction ◽

Synthetic Methods ◽

Copper Hydride ◽

Catalytic Transfer

Catalytic transfer hydrogenations are among the most practical synthetic methods for the selective reduction of functional groups. Cheap and readily available dihydrogen (H2) equivalents are highly desirable for catalytic transfer hydrogenations, as inevitably, waste is generated by the formal H2 source. Copper hydride catalysis generally relies on stoichiometric use of waste-generating hydrosilanes. Here, we demonstrate that simple alcohols can be employed as H2 equivalents in stereoselective alkyne semihydrogenations, prototypical copper hydride-catalysed transformations.

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Copper–Ligand Cooperativity in H2 Activation Enables the Synthesis of Copper Hydride Complexes

10.26434/chemrxiv.13688335.v2 ◽

2021 ◽

Author(s):

Alicia Aloisi ◽

Etienne Crochet ◽

Emmanuel Nicolas ◽

Jean-Claude Berthet ◽

Camille Lescot ◽

...

Keyword(s):

Copper Hydride ◽

Hydride Complexes ◽

Hydride Complex

Copper(I) complexes of a new participative triphosphane ligand (2H) have been prepared and structurally characterized, in particular [Cu(2H)I] and [Cu(2)]2. Hydrogenation of the latter species afforded the trimetallic hydride species [Cu3(2)2(µ-H)] or in the presence of BEt3, [Cu(2H)(HBEt3)]. Their formation evidences transient formation of [Cu(2H)H] formed by hydrogenolysis of the Cu‒ N bond of [Cu(2)]2. [Cu(2H)(HBEt3)] behaves like a hydride complex and inserts CO2 to yield the formate product [Cu(2H)(O2CH)].

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