Iodane-Guided ortho C−H Allylation

Wei W. Chen, Anton Cunillera, Dandan Chen, Sébastien Lethu, Albert López de Moragas, Jun Zhu, Miquel Solà, Ana B. Cuenca, Alexandr Shafir

Research output: Indexed journal article Articlepeer-review

9 Citations (Scopus)

Abstract

A metal-free C−H allylation strategy is described to access diverse functionalized ortho-allyl-iodoarenes. The method employs hypervalent (diacetoxy)iodoarenes and proceeds through the iodane-guided “iodonio-Claisen” allyl transfer. The use of allylsilanes bearing electron-withdrawing functional groups unlocks the functionalization of a broad range of substrates, including electron-neutral and electron-poor rings. The resulting ortho-allylated iodoarenes are versatile building blocks, with examples of downstream transformation including a concise synthesis of the experimental antimitotic core of Dosabulin. DFT calculations shed additional light on the reaction mechanism, with notable aspects including the aromatic character of the transition-state structure for the [3,3] sigmatropic rearrangement, as well as the highly stereoconvergent nature of the trans-product formation.

Original languageEnglish
Pages (from-to)20201-20207
Number of pages7
JournalAngewandte Chemie - International Edition
Volume59
Issue number45
DOIs
Publication statusPublished - 2 Nov 2020

Keywords

  • C−H functionalization
  • allylic compounds
  • arenes
  • hypervalent compounds
  • rearrangements

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