Enantio‐ and Diastereoselective Dehydrative “One‐Step” Construction of Spirocarbocycles via a Ru/H+‐Catalyzed Tsuji–Trost Approach

Abstract

AbstractChiral spirocarbocyclic skeletons are ubiquitous in natural products. An intramolecular Tsuji–Trost (T–T) α‐allylation of simple cyclic ketones is a reasonable approach to construct chiral spriocarbocyclic motifs; however, it has been a challenging approach despite many excellent intermolecular examples. For the first time, this has been achieved by a Ru/H+ combined catalyst that dehydratively cyclizes racemic allylic alcohols comprising a simple ketone via simultaneous activation of the C=O and OH groups. This chiral technology facilitates the construction of various spirocarbocycles containing two contiguous spiro all‐carbon quaternary and tertiary stereocenters. Among four possible stereoisomers, one stereoisomer can be selectively produced in high yield, enhancing the feasibility of the T–T strategy, particularly in the synthesis of spirocarbocycles.