Enantioselective Selenol-ene Using Rh-Hydride Catalysis

Abstract

This study showcases the first enantioselective hydroselenation of styrenes. Organoselenium building blocks are accessed with selectivity for the branched isomer. Through a Rh-hydride pathway, C−Se bonds can be forged with excellent regioand enantiocontrol.

Rh‐Catalyzed Hydroheteroarylation of Styrenes: Access to Alkylated Heteroarenes with All‐Carbon Quaternary Centers

“…In our previous hydrofunctionalization studies, the choice of counterion associated with the Rh center played an important role in the reactivity. [12] On this basis, we evaluated various neutral and cationic rhodium catalysts (entries 2-4). We found Rh(cod) 2 BF 4 catalyzed the hydroheteroarylation to generate the desired alkylated indole 3aa in 93% isolated yield with great selectivity (entry 3).…”

“…To our delight, we found that the desired alkylated indole 3 aa bearing all‐carbon quaternary center at the C3‐position was obtained in 68 % yield by using [Rh(cod)Cl] 2 and thiophenol as co‐catalysts (entry 1). In our previous hydrofunctionalization studies, the choice of counterion associated with the Rh center played an important role in the reactivity [12] . On this basis, we evaluated various neutral and cationic rhodium catalysts (entries 2–4).…”

A rhodium-catalyzed ylide formation/Smiles rearrangement reaction of chalcogenide ether and triazoles

“…insertion, 8 and ylide formation/rearrangement reactions. 9 It is also used frequently for the synthesis of sulfides and selenides via the construction of C(sp 3 )–S/Se bonds, including S–H/Se–H insertion, 10 [2,3]-rearrangement (Doyle–Kirmse rearrangement 11 and Sommelet–Hauser rearrangement), 12 and [1,2]-rearrangement (Stevens rearrangement). 13 However, the method for the construction of C(sp 2 )–S/Se bonds is still rare.…”

Palladium-Catalyzed Enantioselective Hydrosulfonylation of Vinylarenes

“…Any attempt to extend this reaction to vinylarenes would meet with failure because such a process would require a diene moiety for the key hydrogen transfer. In 2022, Dong and Yang reported a Rh–H-catalyzed hydroselenation reaction, and that work represents a precious example of hydrofunctionalization of styrene using chalcogen nucleophile . Nevertheless, the transition-metal-catalyzed asymmetric hydrosulfonylation of vinylarenes remains an unsolved challenge.…”