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Synthesis of tertiary alkyl fluorides and chlorides by site-selective nucleophilic ring-opening reaction of α-aryl azetidinium salts.

ABSTRACT: Site-selective nucleophilic ring-opening reactions of 2-arylazetidine-2-carboxylic acid ester-derived tetraalkyl ammonium salts 2 with tetrabutylammonium halides (Bu₄NX) to give tertiary alkyl halides are successfully demonstrated. For example, a nucleophilic ring-opening reaction of 2-(o-tolyl) derivative 2a with 1.2 equivalents of tetrabutylammonium fluoride (Bu₄NF) in THF at 60 °C preferentially proceeded at a more substituted carbon atom (2-position) compared to a less-substituted carbon atom (4-position) and afforded tert-butyl 4-(dimethylamino)-2-fluoro-2-(o-tolyl)butanoate 3aa in 71% yield as the corresponding tertiary alkyl fluoride. This result was applied to synthesize optically active organofluorine compounds starting from commercially available (R)-1-phenylethylamine.

SUBMITTER: Tayama E

PROVIDER: S-EPMC9044468 | biostudies-literature | 2021 Dec

REPOSITORIES: biostudies-literature

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Synthesis of tertiary alkyl fluorides and chlorides by site-selective nucleophilic ring-opening reaction of α-aryl azetidinium salts.

Tayama Eiji E Kawai Kohei K

RSC advances 20211213 62

Site-selective nucleophilic ring-opening reactions of 2-arylazetidine-2-carboxylic acid ester-derived tetraalkyl ammonium salts 2 with tetrabutylammonium halides (Bu4NX) to give tertiary alkyl halides are successfully demonstrated. For example, a nucleophilic ring-opening reaction of 2-(o-tolyl) derivative 2a with 1.2 equivalents of tetrabutylammonium fluoride (Bu4NF) in THF at 60 °C preferentially proceeded at a more substituted carbon atom (2-position) compared to ...[more]

PMID: 35492462

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