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Preparation of Polyfunctionalized Aromatic Nitriles from Aryl Oxazolines.

ABSTRACT: A selective ortho,ortho'-functionalization of readily available aryl oxazolines by two successive magnesiations with sBu₂ Mg in toluene followed by trapping reactions with electrophiles, such as (hetero)aryl iodides or bromides, iodine, tosyl cyanide, ethyl cyanoformate or allylic bromides (39 examples, 62-99 % yield) is reported. Treatment of these aryl oxazolines with excess oxalyl chloride and catalytic amounts of DMF (50 °C, 4 h) provided the corresponding nitriles (36 examples, 73-99 % yield). Conversions of these nitriles to valuable heterocycles are reported, and a tentative mechanism is proposed.

SUBMITTER: Hess A

PROVIDER: S-EPMC9300023 | biostudies-literature | 2022 Jan

REPOSITORIES: biostudies-literature

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Preparation of Polyfunctionalized Aromatic Nitriles from Aryl Oxazolines.

Hess A A Guelen H C HC Alandini N N Mourati A A Guersoy Y C YC Knochel P P

Chemistry (Weinheim an der Bergstrasse, Germany) 20211202 1

A selective ortho,ortho'-functionalization of readily available aryl oxazolines by two successive magnesiations with sBu<sub>2</sub> Mg in toluene followed by trapping reactions with electrophiles, such as (hetero)aryl iodides or bromides, iodine, tosyl cyanide, ethyl cyanoformate or allylic bromides (39 examples, 62-99 % yield) is reported. Treatment of these aryl oxazolines with excess oxalyl chloride and catalytic amounts of DMF (50 °C, 4 h) provided the corresponding nitriles (36 examples, 7 ...[more]

PMID: 34766655

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