Synthesis and catalytic performance of nickel phosphinite pincer complexes in deoxygenative hydroboration of amides

Adilkhanova, Aziza; Frolova, Valeriya F; Yessengazin, Azamat; Öztopçu, Özgür; Gudun, Kristina; Segizbayev, Medet; Matsokin, Nikita A; Dmitrienko, Anton; Pilkington, Melanie; Khalimon, Andrey Y.

doi:10.1039/d2dt03801c

Dalton Trans.

2023

DOI: 10.1039/d2dt03801c

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Synthesis and catalytic performance of nickel phosphinite pincer complexes in deoxygenative hydroboration of amides

Aziza Adilkhanova

Valeriya F Frolova

Azamat Yessengazin

et al.

Abstract: A series of imino- POCNR, amino- POCNR2, and bis(phosphinite) POCOP pincer complexes of Ni(II) were prepared and tested in catalytic deoxygenative hydroboration of amides with HBPin to the corresponding amines....

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Cited by 4 publications

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Reduction of Carboxamides Into Amines Catalyzed by La[NH‐2,6‐ⁱPr₂‐4‐FcC₆H₂]₃/HBpin

Ye,

Wang,

Chen

et al. 2024

Applied Organom Chemis

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Reduction of carboxamides is an efficient approach to obtain the corresponding amines, albeit it is one of the most problematic. In this work, by use of pinacolborane (HBpin) as a reductant, the rare‐earth metal tris (arylamido) complex supported by a ferrocenyl‐modified arylamido ligand La[NH‐2,6‐iPr2‐4‐FcC6H2]3 was employed as a precatalyst for primary and secondary amide reductions. This catalyst system exhibited high activity toward hydroborative reduction of amides to amines under mild conditions, as well good tolerance for heteroatoms and functional groups in the reduction. A lanthanide hydride was experimentally verified as the active species and the reduction mechanism was proposed.

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Reduction of Carboxamides Into Amines Catalyzed by La[NH‐2,6‐ⁱPr₂‐4‐FcC₆H₂]₃/HBpin

Ye,

Wang,

Chen

et al. 2024

Applied Organom Chemis

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Deoxygenative Reduction of 1°, 2° and 3° Amides via In Situ Generated Tungsten Cluster Acting as H-Bonding Donor

Liu,

Zhai,

Yang

et al. 2024

Org. Lett.

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A protocol of amide-to-amine transformation that is convenient, mild, and easy to perform is a long-sought goal from the viewpoint of catalysis. Herein, we have utilized easily accessible W(CO) 4 (NCMe) 2 as a precatalyst for the deoxygenative reduction of 1°, 2°and 3°amides under mild conditions. Mechanism studies unraveled that the in situ generated W 4 -cluster is potentially a vital species in activating C�O of amides by providing the H-bonding network during the catalytic cycle. Significantly, this tactic offers a complementary pattern to conventional metal-catalyzed amide deoxygenative reactions with activation of the C�O bond via direct coordination with amide.

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Deoxygenation of 1° and 2° Amides with Ce[N(SiMe₃)₂]₃(THF)₃ under Mild Conditions

Hossain,

Shah,

Khan

2023

ACS Catal.

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The development of sustainable methods for the synthesis of amines using commercially available/easy-to-synthesize catalysts under mild conditions is one of the current interests in catalysis. A method of amide-to-amine reduction that is convenient, mild, and easy to implement is a long sought after goal from the catalysis viewpoint. In this work, we have utilized easily accessible Ce[N(SiMe 3 ) 2 ] 3 (THF) 3 as a catalyst for the hydroboration of 1°and 2°amides under mild conditions, which affords corresponding amines in very good yields. It is important to mention that 1°amides are the most difficult to reduce and usually require high temperatures. Further, this methodology is also implemented for the synthesis of indole derivatives and a gramscale reaction, thereby displaying the broad applicability of Ce[N(SiMe 3 ) 2 ] 3 (THF) 3 as a catalyst. A detailed experimental study is performed to understand the mechanistic aspects of the Ce[N(SiMe 3 ) 2 ] 3 (THF) 3 -catalyzed amide hydroboration reaction, which reveals that the formation of an amidate complex is vital for the catalytic cycle.

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Synthesis and catalytic performance of nickel phosphinite pincer complexes in deoxygenative hydroboration of amides

Abstract: A series of imino- POCNR, amino- POCNR2, and bis(phosphinite) POCOP pincer complexes of Ni(II) were prepared and tested in catalytic deoxygenative hydroboration of amides with HBPin to the corresponding amines....

Cited by 4 publications

References 96 publications

Reduction of Carboxamides Into Amines Catalyzed by La[NH‐2,6‐ⁱPr₂‐4‐FcC₆H₂]₃/HBpin

Reduction of Carboxamides Into Amines Catalyzed by La[NH‐2,6‐ⁱPr₂‐4‐FcC₆H₂]₃/HBpin

Deoxygenative Reduction of 1°, 2° and 3° Amides via In Situ Generated Tungsten Cluster Acting as H-Bonding Donor

Deoxygenation of 1° and 2° Amides with Ce[N(SiMe₃)₂]₃(THF)₃ under Mild Conditions

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Synthesis and catalytic performance of nickel phosphinite pincer complexes in deoxygenative hydroboration of amides

Abstract: A series of imino- POCNR, amino- POCNR2, and bis(phosphinite) POCOP pincer complexes of Ni(II) were prepared and tested in catalytic deoxygenative hydroboration of amides with HBPin to the corresponding amines....

Cited by 4 publications

References 96 publications

Reduction of Carboxamides Into Amines Catalyzed by La[NH‐2,6‐iPr2‐4‐FcC6H2]3/HBpin

Reduction of Carboxamides Into Amines Catalyzed by La[NH‐2,6‐iPr2‐4‐FcC6H2]3/HBpin

Deoxygenative Reduction of 1°, 2° and 3° Amides via In Situ Generated Tungsten Cluster Acting as H-Bonding Donor

Deoxygenation of 1° and 2° Amides with Ce[N(SiMe3)2]3(THF)3 under Mild Conditions

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Product

Resources

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Reduction of Carboxamides Into Amines Catalyzed by La[NH‐2,6‐ⁱPr₂‐4‐FcC₆H₂]₃/HBpin

Reduction of Carboxamides Into Amines Catalyzed by La[NH‐2,6‐ⁱPr₂‐4‐FcC₆H₂]₃/HBpin

Deoxygenation of 1° and 2° Amides with Ce[N(SiMe₃)₂]₃(THF)₃ under Mild Conditions