Selective Metalation and Functionalization of Fluorinated Nitriles Using 2,2,6,6-Tetramethylpiperidyl Bases

Selective Metalation and Functionalization of Fluorinated Nitriles Using 2,2,6,6-Tetramethylpiperidyl Bases

We have accomplished regioselective deprotometalation of aromatic and heteroaromatic nitriles via (TMP)2Zn·2MgCl2·2LiCl and TMPMgCl·LiCl (TMP = 2,2,6,6-tetramethylpiperidyl) with the exploration of new and scarcely investigated metalation positions. Regioselectivity was rationalized by DFT calculati...

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Veröffentlicht in:Organic letters 2021-10, Vol.23 (19), p.7396-7400
Hauptverfasser: dos Santos, Thiago, Orenha, Henrique P, Murie, Valter E, Vessecchi, Ricardo, Clososki, Giuliano C
Format: Artikel
Sprache:eng
Schlagworte:
Chemistry
Chemistry, Organic
Physical Sciences
Science & Technology
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Zusammenfassung:We have accomplished regioselective deprotometalation of aromatic and heteroaromatic nitriles via (TMP)2Zn·2MgCl2·2LiCl and TMPMgCl·LiCl (TMP = 2,2,6,6-tetramethylpiperidyl) with the exploration of new and scarcely investigated metalation positions. Regioselectivity was rationalized by DFT calculations. The quenching of the generated organozinc and organomagnesium intermediates with various electrophiles gave access to 47 highly functionalized nitriles with yields up to 95%. Additionally, we report a difunctionalization strategy and the use of functionalized nitriles as building blocks to construct relevant heterocycles.
ISSN:1523-7060
1523-7052
DOI:10.1021/acs.orglett.1c02572