Generation of functionalized asymmetric benzynes with TMP-zincates. Effects of ligands on selectivity and reactivity of zincates

Masanobu Uchiyama, Tomoko Miyoshi, Yumiko Kajihara, Takao Sakamoto, Yuko Otani, Tomohiko Ohwada, Yoshinori Kondo

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161 Citations (Scopus)

Abstract

We have developed new methods for preparing functionalized benzynes through deprotonative zincation as a key reaction using R2Zn(TMP)Li, and we also describes dramatic ligand effects on the benzyne formation. Deprotonative zincation of various meta-substituted bromobenzenes with Me2Zn(TMP)Li proved effective for the one-pot generation of various 3-functionalized benzynes, particularly those electrophilic substituents such as ester, amide, and cyano. On the other hand, zincation with tBu2Zn(TMP)Li, followed by electrophilic trapping (with I2) proved a powerful tool for the preparation of 1,2,3-trisubstituted aromatic compounds.8 The resultant 1,2,3-trisubstituted benzenes are available as precursors for generation of 3-substituted benzynes by halogen-zinc exchange reactions with Me3ZnLi. These methods offer far greater generality than previous methods for the synthesis of functionalized asymmetric benzynes, and should be of value in new syntheses of various natural products and functional materials. In addition, these results underline the utility of spectator ligands on the central metal of ate complexes as a tunable functionality in the development of new ate complex-promoted reactions.

Original languageEnglish
Pages (from-to)8514-8515
Number of pages2
JournalJournal of the American Chemical Society
Volume124
Issue number29
DOIs
Publication statusPublished - 2002 Jul 24

ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry

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