Disproportionation-Inspired Construction of Highly Functionalized Bicyclo[3.2.1]octanes

Abstract

The formation of one unavoidable byproduct in traditional disproportionation reactions limits their applications in synthesis. Inspired by convergent disproportionation, we develop an iodine-induced cyclization and oxidation of allylic alcohols to produce highly functionalized bicyclo[3.2.1]octanes through creation of six new bonds. Guided by the mechanism, we elaborated a variety of other bicyclo[3.2.1]octanes bearing distinct groups with presynthesized dienes and enones as the starting materials. This work provides a divergent access to bicyclo[3.2.1]octane frameworks.

Cross-Electrophile Coupling of Benzyl Halides and Disulfides Catalyzed by Iron

“…As an essential element for deoxyribonucleic acid (DNA) synthesis, oxygen transport, and electron transport, among other metabolic processes, 33,34 iron is also vital to most living organisms and lowly toxic. 35 Current synthetic methods for thioether synthesis are limiting 36 with methods primarily relying on harsh basic or acidic conditions, 37,38 giving rise to undesired byproducts. Specifically, substrates containing homobenzylic protons are vulnerable to elimination reaction pathways under such conditions.…”

“…Current synthetic methods for thioether synthesis are limiting with methods primarily relying on harsh basic or acidic conditions, , giving rise to undesired byproducts. Specifically, substrates containing homobenzylic protons are vulnerable to elimination reaction pathways under such conditions.…”

Dual Photoredox/Nickel-Catalyzed Dehydrative Difluoroalkylation of Benzyl Alcohols for the Synthesis of Allylic gem-Difluorides

“…On the other hand, alcohols are some of the most widely used feedstocks, and they are also considered to be important sources of alkenes for both academic and industrial applications. Over the past decade, a series of reports on deoxygenative transformations of alcohols via alkene intermediates have been described, including asymmetric hydrogenation, dehydrative alkylation, intermolecular cyclization, and the construction of sp 2 or sp 3 C–P bonds . Despite the above advances in this concept, the synthesis of allylic gem -difluorides via alcohols remains an uncharted territory.…”

Cross-Electrophile Coupling of Benzyl Halides and Disulfides Catalyzed by Iron

“…Current synthetic methods for thioether synthesis are limiting 36 with methods primarily relying on harsh basic or acidic conditions, 37,38 giving rise to undesired byproducts. Specifically, benzylic substrates containing a homobenzylic proton are vulnerable to elimination reaction pathways under such conditions.…”