σ-Bond Hydroboration of Cyclopropanes

Hiroki Kondo, Shin Miyamura, Kaoru Matsushita, Hiroki Kato, Chisa Kobayashi, Arifin, Kenichiro Itami, Daisuke Yokogawa, Junichiro Yamaguchi

Research output: Contribution to journalArticlepeer-review

Abstract

Hydroboration of alkenes is a classical reaction in organic synthesis in which alkenes react with boranes to give alkylboranes with subsequent oxidation resulting in alcohols. The double bond (π-bond) of alkenes can be readily reacted with boranes owing to its high reactivity. However, the single bond (σ-bond) of alkanes has never been reacted. To pursue the development of σ-bond cleavage, we selected cyclopropanes as model substrates since they present a relatively weak σ-bond. Herein, we describe an iridium-catalyzed hydroboration of cyclopropanes, resulting in β-methyl alkylboronates. These unusually branched boronates can be derivatized by oxidation or cross-coupling chemistry, accessing "designer"products that are desired by practitioners of natural product synthesis and medicinal chemistry. Furthermore, mechanistic investigations and theoretical studies revealed the enabling role of the catalyst.

Original languageEnglish
Pages (from-to)11306-11313
Number of pages8
JournalJournal of the American Chemical Society
Volume142
Issue number25
DOIs
Publication statusPublished - 2020 Jun 24

ASJC Scopus subject areas

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

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