Ni-catalyzed hydroaminoalkylation of alkynes with amines

Yao, Weiwei; Li, Ran; Chen, Hao; Chen, Ming-Kai; Luan, Yu‐Xin; Wang, Yi; Yu, Zhi‐Xiang; Ye, Mengchun

doi:10.1038/s41467-021-24032-9

Cited by 16 publications

(3 citation statements)

References 55 publications

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“…Late transition-metal-catalyzed hydroaminoalkylation of alkynes has been reported by the Ye group. 134 Using an in situ prepared catalyst system with Ni(COD) 2 , PCy 3 as a phosphine, and IPr as an NHC ligand, substituted allylamine products can be prepared (Scheme 35). Similar to Zr-based work from our lab, 89 this paper focuses on protected primary amine substrates with internal alkyne coupling partners.…”

Section: Modifying Reactivity Bymentioning

confidence: 99%

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Hydroaminoalkylation for the Catalytic Addition of Amines to Alkenes or Alkynes: Diverse Mechanisms Enable Diverse Substrate Scope

2022

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Hydroaminoalkylation is a powerful, atom-economic catalytic reaction for the reaction of amines with alkenes and alkynes. This C–H functionalization reaction allows for the atom-economic alkylation of amines using simple alkenes or alkynes as the alkylating agents. This transformation has significant potential for transformative approaches in the pharmaceutical, agrochemical, and fine chemical industries in the preparation of selectively substituted amines and N-heterocycles and shows promise in materials science for the synthesis of functional and responsive aminated materials. Different early transition-metal, late transition-metal, and photoredox catalysts mediate hydroaminoalkylation by distinct mechanistic pathways. These mechanistic insights have resulted in the development of new catalysts and reaction conditions to realize hydroaminoalkylation with a broad range of substrates: activated and unactivated, terminal and internal, C–C double and triple bonds with aryl or alkyl primary, secondary, or tertiary amines, including N-heterocyclic amines. By deploying select catalysts with specific substrate combinations, control over regioselectivity, diastereoselectivity, and enantioselectivity has been realized. Key barriers to widespread adoption of this reaction include air and moisture sensitivity for early transition-metal catalysts as well as a heavy dependence on amine protecting or directing groups for late transition-metal or photocatalytic routes. Advances in improved catalyst robustness, substrate scope, and regio-/stereoselective reactions with early- and late transition-metal catalysts, as well as photoredox catalysis, are highlighted, and opportunities for further catalyst and reaction development are included. This perspective shows that hydroaminoalkylation has the potential to be a disruptive and transformative strategy for the synthesis of selectively substituted amines and N-heterocycles from simple amines and alkenes.

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Section: Modifying Reactivity Bymentioning

confidence: 99%

“…Late transition-metal-catalyzed hydroaminoalkylation of alkynes has been reported by the Ye group . Using an in situ prepared catalyst system with Ni(COD) 2 , PCy 3 as a phosphine, and IPr as an NHC ligand, substituted allylamine products can be prepared (Scheme ).…”

Section: Late Transition-metal-catalyzed Hydroaminoalkylationmentioning

confidence: 99%

Hydroaminoalkylation for the Catalytic Addition of Amines to Alkenes or Alkynes: Diverse Mechanisms Enable Diverse Substrate Scope

2022

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“…In previous examples of imine and alkyne reductive coupling reactions, a terminal reductant such as H 2 or a H 2 surrogate is used, and the products contain a hydrogen atom at the site of the M–C bond . The same process has also been achieved in a redox-neutral fashion using an amine and an alkyne through a hydrogen borrowing strategy . Alternatively, there are limited cases where a third organoboron component can be introduced to carry out tandem oxidative cyclization and C–C cross-coupling. , Finally, there is a singular example of transmetalation to form an aluminum metallacycle .…”

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confidence: 99%

Catalytic Asymmetric Synthesis of Zinc Metallacycles

Bishop,

Zhao,

Uyeda

2023

J. Am. Chem. Soc.

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Transition-metal-catalyzed reductive coupling reactions of alkynes and imines are attractive methods for the synthesis of chiral allylic amines. Mechanistically, these reactions involve oxidative cyclization of the alkyne and the imine to generate a metallacyclic intermediate, which then reacts with H2 or a H2 surrogate to form the product. As an alternative to this hydrogenolysis pathway, here we show that transmetalation to zinc can occur, forming a zinc metallacycle product. This organozinc product serves as a versatile nucleophile for carbon–carbon and carbon–heteroatom coupling reactions. Mechanistic studies based on isotopic labeling experiments and DFT calculations suggest that the key transmetalation step occurs between a Co(II) species and ZnCl2.

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Nickel‐Catalyzed Intermolecular Branched/Linear Regioselective C−H Alkylation of 4‐Oxoquinazolines

et al. 2023

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A Ni−NHC‐catalyzed prototype reaction based on the alkylation of C−H activated 4‐oxoquinazolines with aryl and alkyl alkenes was demonstrated. When aryl alkenes are used as the substrates, the regioselection of the reaction can be fine‐tuned by choosing a NHC ligand with appropriate steric hindrance to harvest branched adducts, while the use of a bulky NHC/alkyl aluminum cocatalyst system helps to steer the reaction towards linear products. For alkyl alkene substrates, Ni(cod)2, IMes ⋅ HCl and NaOtBu system can directionally generate linear products, and long‐chain olefins are also applicable. In addition, the catalytic mechanism was also explored through the deuteration experiments, and the migration of nickel was suggested in the catalytic cycle.

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Ni-catalyzed hydroaminoalkylation of alkynes with amines

Cited by 16 publications

References 55 publications

Hydroaminoalkylation for the Catalytic Addition of Amines to Alkenes or Alkynes: Diverse Mechanisms Enable Diverse Substrate Scope

Hydroaminoalkylation for the Catalytic Addition of Amines to Alkenes or Alkynes: Diverse Mechanisms Enable Diverse Substrate Scope

Catalytic Asymmetric Synthesis of Zinc Metallacycles

Nickel‐Catalyzed Intermolecular Branched/Linear Regioselective C−H Alkylation of 4‐Oxoquinazolines

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