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σ-Bond Hydroboration of Cyclopropanes
preprintsubmitted on 07.01.2020, 14:16 and posted on 08.01.2020, 21:12 by Hiroki Kondo, Shin Miyamura, Chisa Kobayashi, Arifin, Stephan Irle, Kenichiro Itami, Daisuke Yokogawa, Junichiro Yamaguchi
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.