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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 journal › Article › peer-review
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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