Highly Diastereoselective Preparation of Tertiary Alkyl Thiocyanates en Route to Thiols by Stereoinvertive Nucleophilic Substitution at Nonclassical Carbocations.

An effective InBr-catalyzed nucleophilic thiocyanation of cyclopropyl alcohols has been developed. The reaction takes place at the quaternary carbon stereocenter of the cyclopropyl carbinol with a complete inversion of configuration, offering a novel pathway for the creation of complex tertiary alkyl thiocyanates with high diastereopurity. These substitution reactions proceed under mild reaction conditions and tolerate several functional groups.

Stereoselective Construction of Tertiary Homoallyl Alcohols and Ethers by Nucleophilic Substitution at Quaternary Carbon Stereocenters.

An efficient method for the stereoselective construction of tertiary C-O bonds via a stereoinvertive nucleophilic substitution at the quaternary carbon stereocenter of cyclopropyl carbinol derivatives using water, alcohols and phenols as nucleophiles has been developed. This substitution reaction proceeds under mild conditions and tolerates several functional groups, providing a new access to the stereoselective formation of highly congested tertiary homoallyl alcohols and ethers.

Stereospecific Construction of Quaternary Carbon Stereocenters from Quaternary Carbon Stereocenters.

Organoaluminum species promote a smooth nucleophilic substitution at the quaternary carbon stereocenter of stereodefined polysubstituted cyclopropyl methyl phosphate with a complete inversion of configuration, even when more reactive functional groups are present. The regio- and diastereoselectivity of the substitution is attributed to the existence of a bicyclobutonium intermediate.

Ring-Opening/Recyclization Cascades of Monoactivated Cyclopropanes.

A variety of cyclopropyl aryl ketones undergo uncatalyzed cascade ring-opening/recyclization reactions to generate indenones and fluorenones. In addition, a new strategy to access 3-hydroxyindanones possessing two contiguous stereogenic centers, one of them being an all-carbon quaternary center, was also established. During the course of the investigation, pronounced solvent, temperature, and substituent effects on the product distribution were discovered.

Beyond the Corey-Chaykovsky Reaction: Synthesis of Unusual Cyclopropanoids via Desymmetrization and Thereof.

Desymmetrization-based protocols for the synthesis of highly functionalized indeno-spirocyclopropanes and cyclopropa-fused indanes have been established through unexpected reactions triggered by the Corey-Chaykovsky reagent. These structures were further elaborated in one step to privileged scaffolds such as fluorenones, indenones, and naphthaphenones. For instance, an acid-catalyzed transformation of indeno-spirocyclopropanes provided fluorenones via a homo-Nazarov-type cyclization, and naphthaphenones were obtained via an acid-catalyzed cyclopropane ring-opening/retro-Michael sequence.

Synthesis of Cyclopropanoids via Substrate-Based Cyclization Pathways.

A series of unexpected reactions triggered by the dimethyloxosulfonium methylide led to the discovery of unconventional approaches for the synthesis of cyclopropa-fused tetralones and indeno-spirocyclopropanes. These highly functionalized structures were further elaborated in one step to privileged scaffolds such as tetralones, indenones, and fluorenones. As a whole, the results presented herein establish new diversity-oriented folding pathways.