Rhodium-Catalyzed Asymmetric Arylative Ring-Opening Reactions of Heterobicyclic Alkenes with Anilines

Asymmetric arylative ring-opening reactions of heterobicyclic alkenes with anilines have been reported for the first time. A wide range of heterobicyclic alkenes, including azabenzonorbornadienes and oxabenzonorbornadienes, were well tolerated in the reaction with various anilines, and they generally delivered the corresponding chiral aryltetralin derivatives in good to excellent enantioselectivities. The reaction is speculated to proceed through the Friedel–Crafts reaction pathway

Iridium-Catalyzed Anti-Stereoselective Asymmetric Ring-Opening Reactions of Azabenzonorbornadienes with Carboxylic Acids

The first anti-stereoselective asymmetric ring-opening reactions of azabenzonorbornadienes with carboxylic acids have been realized with an iridium catalyst assisted by ^<i>n</i>Bu₄NBr. The reaction features broad substrate scope and good functional group tolerance and allows the synthesis of chiral dihydronaphthalene derivatives with high optical purities

Rhodium-Catalyzed Asymmetric Cyclization/Addition Reactions of 1,6-Enynes and Oxa/Azabenzonorbornadienes

A mild, efficient, and novel rhodium catalyzed asymmetric cyclization–addition domino reaction of oxa/azabenzonorbornadienes and 1,6-enynes is documented. Through the use of a [Rh­(COD)₂]­BF₄-(<i>R</i>)-An-SDP catalytic system, highly enantioenriched cyclization–addition products were obtained in good yields and with excellent enantioselectivities

Palladium/Silver-Cocatalyzed Tandem Reactions of Oxabenzonorbornadienes with Substituted Arylacetylenes: A Simple Method for the Preparation of 1,2-Diarylethanones and 1,2-Diarylacetylenes

The effective synthesis of 1,2-diarylethanones was achieved using palladium­(II) acetate [Pd­(OAc)₂] and silver triflate (AgOTf) as cocatalysts from various oxabenzonorbornadiene derivatives and substituted arylacetylenes via tandem reactions under mild conditions. Exploration of the oxabenzonorbornadiene substrates showed that the 1,2-diarylacetylenes were obtained from adjacent alkoxy substituted oxabenzonorbornadiene derivatives. Preliminary mechanistic studies indicate that the AgOTf served as an indispensable catalyst, and the mechanism of the tandem reaction was proposed

Asymmetric Ring-Opening Reactions of Aza- and Oxa-bicyclic Alkenes with Boronic Acids Using a Palladium/Zinc Co-catalytic System

The asymmetric ring opening reactions of bicyclic alkenes with boronic acids were accomplished by using a highly active palladium/zinc co-catalytic system that was suitable for both azabenzonorbornadienes and oxabenzonorbornadienes, which were transformed to the corresponding chiral hydronaphthalene products in high yields (up to 99%) and high optical purities (up to 98% ee). The reaction protocol is general and mild and displays good functional group tolerance