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Lipshutz-type bis(amido)argentates for directed ortho argentation.

ABSTRACT: Bis(amido)argentate (TMP)₂Ag(CN)Li₂ (3, TMP-Ag-ate; TMP = 2,2,6,6-tetramethylpiperidido) was designed as a tool for chemoselective aromatic functionalization via unprecedented directed ortho argentation (DoAg). X-Ray crystallographic analysis showed that 3 takes a structure analogous to that of the corresponding Lipshutz cuprate. DoAg with this TMP-Ag-ate afforded multifunctional aromatics in high yields in processes that exhibited high chemoselectivity and compatibility with a wide range of functional groups. These included organometallics- and transition metal-susceptible substituents such as methyl ester, aldehyde, vinyl, iodo, (trifluoromethanesulfonyl)oxy and nitro groups. The arylargentates displayed good reactivity with various electrophiles. Chalcogen (S, Se, and Te) installation and azo coupling reactions also proceeded efficiently.

SUBMITTER: Tezuka N

PROVIDER: S-EPMC8148356 | biostudies-literature | 2020 Jan

REPOSITORIES: biostudies-literature

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Lipshutz-type bis(amido)argentates for directed ortho argentation.

Tezuka Noriyuki N Hirano Keiichi K Peel Andrew J AJ Wheatley Andrew E H AEH Miyamoto Kazunori K Uchiyama Masanobu M

Chemical science 20200107 7

Bis(amido)argentate (TMP)2Ag(CN)Li2 (3, TMP-Ag-ate; TMP = 2,2,6,6-tetramethylpiperidido) was designed as a tool for chemoselective aromatic functionalization via unprecedented directed ortho argentation (DoAg). X-Ray crystallographic analysis showed that 3 takes a structure analogous to that of the corresponding Lipshutz cuprate. DoAg with this TMP-Ag-ate afforded multifunctional aromatics in high yields in processes that exhibited ...[more]

PMID: 34123279

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