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

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

Journal

Tetrahedron
ISSN: 0040-4020

Output data

Year: 2018, Volume: 74, Number: 8, Pages: 842-851 Pages count : 10 DOI: 10.1016/j.tet.2017.12.046

Tags

Reductive alkylation; Biphenyl-4-carbonitrile; Dianion; Cyclohexadienyl anions; Nucleophilic substitution

Authors

Fedyushin Pavel A. ¹ , Peshkov Roman Yu. ^1,2 , Panteleeva Elena V. ^1,2 , Tretyakov Evgeny V. ^1,2 , Beregovaya Irina V. ¹ , Gatilov Yuri V. ^1,2 , Shteingarts Vitalij D. ¹

Affiliations

1	(Данные Web of science) Russian Acad Sci, NN Vorozhtsov Inst Organ Chem, Siberian Branch, Ac Lavrentiev Ave 9, Novosibirsk 630090, Russia
2	(Данные Web of science) Novosibirsk State Univ, Pirogova Str 2, Novosibirsk 630090, Russia

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). (C) 2017 Elsevier Ltd. All rights reserved.

Fedyushin P.A. , Peshkov R.Y. , Panteleeva E.V. , Tretyakov E.V. , Beregovaya I.V. , Gatilov Y.V. , Shteingarts V.D.
Purposeful regioselectivity control of the Birch reductive alkylation of biphenyl-4-carbonitrile
Tetrahedron. 2018. V.74. N8. P.842-851. DOI: 10.1016/j.tet.2017.12.046 WOS Scopus

Published print:

Feb 1, 2018

Web of science	WOS:000425197700006
Scopus	2-s2.0-85040532163
OpenAlex	W2777873477