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Purposeful regioselectivity control of the Birch reductive alkylation of biphenyl-4-carbonitrile. / Fedyushin, Pavel A.; Peshkov, Roman Yu; Panteleeva, Elena V. et al.

In: Tetrahedron, Vol. 74, No. 8, 22.02.2018, p. 842-851.

Research output: Contribution to journalArticlepeer-review

Harvard

Fedyushin, PA, Peshkov, RY, Panteleeva, EV, Tretyakov, EV, Beregovaya, IV, Gatilov, YV & Shteingarts, VD 2018, 'Purposeful regioselectivity control of the Birch reductive alkylation of biphenyl-4-carbonitrile', Tetrahedron, vol. 74, no. 8, pp. 842-851. https://doi.org/10.1016/j.tet.2017.12.046

APA

Fedyushin, P. A., Peshkov, R. Y., Panteleeva, E. V., Tretyakov, E. V., Beregovaya, I. V., Gatilov, Y. V., & Shteingarts, V. D. (2018). Purposeful regioselectivity control of the Birch reductive alkylation of biphenyl-4-carbonitrile. Tetrahedron, 74(8), 842-851. https://doi.org/10.1016/j.tet.2017.12.046

Vancouver

Fedyushin PA, Peshkov RY, Panteleeva EV, Tretyakov EV, Beregovaya IV, Gatilov YV et al. Purposeful regioselectivity control of the Birch reductive alkylation of biphenyl-4-carbonitrile. Tetrahedron. 2018 Feb 22;74(8):842-851. doi: 10.1016/j.tet.2017.12.046

Author

BibTeX

@article{1c131a025e2c4016bce37023d6b50670,
title = "Purposeful regioselectivity control of the Birch reductive alkylation of biphenyl-4-carbonitrile",
abstract = "Birch's reductive alkylation of biphenyl-4-carbonitrile (1) provides alkylated 1,4-dihydroderivatives of various structural types: 4-alkyl-4-phenylcyclohexa-2,5-dienone, 1,4-dialkyl-4-phenylcyclohexa-2,5-dienecarbonitrile (with the same or different alkyl fragments), and 4-(1-alkylcyclohexa-2,5-dienyl)benzonitrile. Each of these products become dominant depending on the nature of long-living anionic form generated from 1, namely, the stable product of two-electrons reduction - dianion (1 2- ); 1-alkyl-4-cyano-1-phenylcyclohexa-2,5-dien-4-yl anion (1-Alk 1 - ), originated due to the alkylation of dianion 1 2- at the position 1 of biphenyl moiety; or 1-(4-cyanophenyl)cyclohexa-2,5-dien-1-yl anion (1-H 4' - ), being the product of dianion 1 2- protonation at position 4' by protonating reagent (MeOH or NH4Cl). The orientation of alkyl fragment incorporation into biphenyl-4-carbonitrile scaffold is in agreement with calculated electronic structure of the anionic species under investigation. The dominating type of their reactivity towards alkyl halides proved to be nucleophilic (S N 2 mechanism).",
keywords = "Biphenyl-4-carbonitrile, Cyclohexadienyl anions, Dianion, Nucleophilic substitution, Reductive alkylation, METAL-AMMONIA REDUCTION, NATURAL-PRODUCTS, ELECTROCHEMICAL REDUCTION, AROMATIC-COMPOUNDS, LIQUID-AMMONIA, ANIONIC PRODUCTS, 2-ELECTRON REDUCTION, CROSS-COUPLING REACTIONS, SYNTHETIC APPLICATIONS, ELECTRONIC-STRUCTURE",
author = "Fedyushin, {Pavel A.} and Peshkov, {Roman Yu} and Panteleeva, {Elena V.} and Tretyakov, {Evgeny V.} and Beregovaya, {Irina V.} and Gatilov, {Yuri V.} and Shteingarts, {Vitalij D.}",
note = "Publisher Copyright: {\textcopyright} 2017 Elsevier Ltd",
year = "2018",
month = feb,
day = "22",
doi = "10.1016/j.tet.2017.12.046",
language = "English",
volume = "74",
pages = "842--851",
journal = "Tetrahedron",
issn = "0040-4020",
publisher = "Elsevier",
number = "8",

}

RIS

TY - JOUR

T1 - Purposeful regioselectivity control of the Birch reductive alkylation of biphenyl-4-carbonitrile

AU - Fedyushin, Pavel A.

AU - Peshkov, Roman Yu

AU - Panteleeva, Elena V.

AU - Tretyakov, Evgeny V.

AU - Beregovaya, Irina V.

AU - Gatilov, Yuri V.

AU - Shteingarts, Vitalij D.

N1 - Publisher Copyright: © 2017 Elsevier Ltd

PY - 2018/2/22

Y1 - 2018/2/22

N2 - Birch's reductive alkylation of biphenyl-4-carbonitrile (1) provides alkylated 1,4-dihydroderivatives of various structural types: 4-alkyl-4-phenylcyclohexa-2,5-dienone, 1,4-dialkyl-4-phenylcyclohexa-2,5-dienecarbonitrile (with the same or different alkyl fragments), and 4-(1-alkylcyclohexa-2,5-dienyl)benzonitrile. Each of these products become dominant depending on the nature of long-living anionic form generated from 1, namely, the stable product of two-electrons reduction - dianion (1 2- ); 1-alkyl-4-cyano-1-phenylcyclohexa-2,5-dien-4-yl anion (1-Alk 1 - ), originated due to the alkylation of dianion 1 2- at the position 1 of biphenyl moiety; or 1-(4-cyanophenyl)cyclohexa-2,5-dien-1-yl anion (1-H 4' - ), being the product of dianion 1 2- protonation at position 4' by protonating reagent (MeOH or NH4Cl). The orientation of alkyl fragment incorporation into biphenyl-4-carbonitrile scaffold is in agreement with calculated electronic structure of the anionic species under investigation. The dominating type of their reactivity towards alkyl halides proved to be nucleophilic (S N 2 mechanism).

AB - Birch's reductive alkylation of biphenyl-4-carbonitrile (1) provides alkylated 1,4-dihydroderivatives of various structural types: 4-alkyl-4-phenylcyclohexa-2,5-dienone, 1,4-dialkyl-4-phenylcyclohexa-2,5-dienecarbonitrile (with the same or different alkyl fragments), and 4-(1-alkylcyclohexa-2,5-dienyl)benzonitrile. Each of these products become dominant depending on the nature of long-living anionic form generated from 1, namely, the stable product of two-electrons reduction - dianion (1 2- ); 1-alkyl-4-cyano-1-phenylcyclohexa-2,5-dien-4-yl anion (1-Alk 1 - ), originated due to the alkylation of dianion 1 2- at the position 1 of biphenyl moiety; or 1-(4-cyanophenyl)cyclohexa-2,5-dien-1-yl anion (1-H 4' - ), being the product of dianion 1 2- protonation at position 4' by protonating reagent (MeOH or NH4Cl). The orientation of alkyl fragment incorporation into biphenyl-4-carbonitrile scaffold is in agreement with calculated electronic structure of the anionic species under investigation. The dominating type of their reactivity towards alkyl halides proved to be nucleophilic (S N 2 mechanism).

KW - Biphenyl-4-carbonitrile

KW - Cyclohexadienyl anions

KW - Dianion

KW - Nucleophilic substitution

KW - Reductive alkylation

KW - METAL-AMMONIA REDUCTION

KW - NATURAL-PRODUCTS

KW - ELECTROCHEMICAL REDUCTION

KW - AROMATIC-COMPOUNDS

KW - LIQUID-AMMONIA

KW - ANIONIC PRODUCTS

KW - 2-ELECTRON REDUCTION

KW - CROSS-COUPLING REACTIONS

KW - SYNTHETIC APPLICATIONS

KW - ELECTRONIC-STRUCTURE

UR - http://www.scopus.com/inward/record.url?scp=85040532163&partnerID=8YFLogxK

U2 - 10.1016/j.tet.2017.12.046

DO - 10.1016/j.tet.2017.12.046

M3 - Article

AN - SCOPUS:85040532163

VL - 74

SP - 842

EP - 851

JO - Tetrahedron

JF - Tetrahedron

SN - 0040-4020

IS - 8

ER -

ID: 12100297