Catalytic Enantioselective Construction of Chiral γ-Azido Nitriles through Nitrile Group-Promoted Electrophilic Reaction of Alkenes

Abstract

An efficient approach for the construction of enantioenriched γ-azido nitriles through the chiral sulfide-catalyzed asymmetric electrophilic thioazidation of allylic nitriles is disclosed. A wide range of electron-deficient and -rich aryl, heterocyclic aryl, and alkyl substituents are suitable on the substrates of allylic nitriles. The regio-, enantio-, and diastereoselectivities of the reactions are excellent. As versatile platform molecules, the obtained chiral γ-azido nitriles can be easily converted into high-valueadded chiral molecules that are not easily accessed by other methods. Control experiments revealed that the allylic nitrile group is important for control of the reactivity and enantioselectivity of the reaction leading to a broad substrate scope.

Catalytic Enantioselective Aminative Difunctionalization of Alkenes

“…Our group has been working on electrophilic reactions. ,, As part of our continuous interest in it, electrophilic aminative difunctionalization of alkenes became our next goal. We proposed that enantioenriched nitrogen-containing molecules such as organic hydrazine derivatives might be formed via catalytic enantioselective electrophilic aminative difunctionalization of unactivated alkenes using external azo compounds as nitrogen sources.…”

Catalytic Enantioselective Electrophilic Difunctionalization of Unsaturated Sulfones

“…Different groups over the world have utilized this strategy to realize the conversion of various alkenes in the past years. As a part of our research, our group has disclosed catalytic enantioselective electrophilic thiolative difunctionalization of allylic sulfonamides and nitriles . In these transformations, an electron-withdrawing group needs to be installed at the allylic position on the substrates to achieve the high enantioselectivities of the reactions.…”