Copper-promoted cyanation of aryl iodides with N,N-dimethyl aminomalononitrile

Liu, Si-Zhan; Li, Jing; Xue, Cao-Gen; Xu, Xuetao; Lei, Lin-sheng; Huo, Chen-Yu; Wang, Zhen; Wang, Shao‐Hua

doi:10.1016/j.tetlet.2020.152749

Cited by 7 publications

(3 citation statements)

References 68 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Following the general procedure with 1-bromonaphthalene provided the desired product as a colorless powder in 43% yield, and naphthalene was isolated in 46% yield (163 mg, 1.08 mmol): 1 H NMR (400 MHz, chloroform- d ) δ 8.27 (d, J = 8.4 Hz, 1H), 8.11 (d, J = 8.3 Hz, 1H), 8.00–7.92 (m, 2H), 7.78–7.69 (m, 1H), 7.69–7.62 (m, 1H), 7.55 (dd, J = 8.3, 7.2 Hz, 1H); 13 C{ 1 H} NMR (101 MHz, chloroform- d ) δ 133.29, 132.94, 132.64, 132.38, 128.67, 128.62, 127.57, 125.18, 124.94, 117.83, 110.23. Spectra matched those previously reported …”

Section: Methodssupporting

confidence: 87%

“…Spectra matched those previously reported. 28 2-Naphthonitrile (4). Following the general procedure with 2bromonaphthalene provided the desired product as a colorless powder in 48% yield as determined by NMR: 1 H NMR (500 MHz, chloroform-d) δ 8.27 (d, J = 1.5 Hz, 1H), 8.09−7.84 (m, 3H), 7.68 (ddd, J = 8.4, 6.9, 1.4 Hz, 1H), 7.64 (ddt, J = 7.9, 3.6, 1.8 Hz, 2H); 21 1-Methyl-1H-indole-2-carbonitrile (5).…”

Section: Synthesis Of Aibn-d 12mentioning

confidence: 99%

See 1 more Smart Citation

AIBN as an Electrophilic Reagent for Cyano Group Transfer

Elliott

Alabugin

2023

J. Org. Chem.

View full text Add to dashboard Cite

AIBN is a convenient electrophilic cyanation reagent for transforming ArLi into ArCN under mild conditions. The addition/ fragmentation cascade is controlled by Li•••N chelation in which AIBN nitrogens assist in the nearly barrierless fragmentation into the desired ArCN product. Acidic C−H bonds in the fragmented byproduct partially consume ArLi by protonation. Density functional theory calculations and isotopic labeling probe the mechanism and explain the switch to substituted hydrazones in reactions with BuLi.

show abstract

Section: Methodssupporting

confidence: 87%

Section: Synthesis Of Aibn-d 12mentioning

confidence: 99%

AIBN as an Electrophilic Reagent for Cyano Group Transfer

Elliott

Alabugin

2023

J. Org. Chem.

View full text Add to dashboard Cite

show abstract

“…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