Synthesis of Two Types of Nitriles Both Bearing Quaternary Carbon Centers in One-Pot Manner

Ren, Xinyi; Wang, Guangzhu; Ji, Xiaolei; Dong, Kaiwu

doi:10.6023/cjoc202107017

Search citation statements

Order By: Relevance

Paper Sections

Select...

Introduction1

Citation Types

Supporting

Mentioning

Contrasting

Year Published

2023

Publication Types

Select...

Article1

Relationship

Self Cite0

Independent1

Authors

Journals

Cited by 1 publication

(1 citation statement)

References 51 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…The π-electrophilicity of malononitriles has been used for transnitrilation (nitrile-transfer) reactions that deploy malononitriles as C-bound sources of CN. − Our group has recently reported the use of 2-methyl-2-phenylmalononitrile (MPMN) for an efficient Ni-catalyzed reductive cyanation of aryl (pseudo)halides . The successful application of MPMN as a π-electrophilic CN source prompted us to explore its reactivity with other amenable reaction partners.…”

Section: Introductionmentioning

confidence: 99%

Nickel-Catalyzed Reductive Alkyne Hydrocyanation Enabled by Malononitrile and a Formaldehyde Additive

Palermo,

Chiu,

Patel

et al. 2023

J. Am. Chem. Soc.

View full text Add to dashboard Cite

The development of a nickel-catalyzed reductive alkyne hydrocyanation is described using 2-methyl-2-phenylmalononitrile (MPMN), a C-bound electrophilic transnitrilation reagent. Reproducibility issues led to the detection of oxidized hemiaminal impurities within N,N-dimethylacetamide. These impurities release formaldehyde in situ, which was ultimately identified as a critical reaction additive. A range of diaryl and aryl-alkyl alkynes underwent hydrocyanation. Mechanistic experiments revealed that formaldehyde and MPMN undergo a Ni-catalyzed reductive coupling of two π-components, leading to the controlled release of glycolonitrile as the active cyanating agent.

show abstract