Dual Catalysis Becomes Diastereodivergent

Abstract

Diastereodivergent is cool: The development of catalytic systems able to generate each and every one of the possible product diastereoisomers from the same starting materials (i.e., that are “diastereodivergent”) is an emerging field in asymmetric catalysis. The possibility of designing such systems in a rational manner based on dual catalysis has now become reality

Organocatalytic Asymmetric α-Chlorination of 1,3-Dicarbonyl Compounds Catalyzed by 2-Aminobenzimidazole Derivatives

“…This assumption was based on the fact that the reaction using catalyst 1 with NCS and 2,3,4,5,6,6-hexachlorocyclohexa-2,4-dienone as chlorine source rendered the corresponding product 5a with opposite configurations. The same stereodivergent [38][39][40][41][42] behavior was observed with catalyst 2.…”

“…the corresponding product 5a with opposite configurations. The same stereodivergent [38][39][40][41][42] behavior was observed with catalyst 2. Finally, and based on previous studies from our group on which chiral 2-aminobenzimidazolederived organocatalysts were employed in different reactions, tentative mechanisms can be proposed for methods A and B (Figures 2 and 3).…”

Catalytic Strategies for Diastereodivergent Synthesis

“…Carreira introduced the concept of stereodivergent dual catalysis to the enantioselective synthesis. The crux of the concept is that two chiral catalysts activate independently and simultaneously both reaction partners, thus the absolute configuration of the respective catalyst can control absolutely over the stereocenter originated from the fragment it activates.…”

Organocatalytic Enantioselective Regiodivergent C−H Bond Functionalization of 1‐Naphthols with 1‐Azadienes

“…[1] Benefitting from the advance in the field of asymmetric catalysis, an abundant range of enantiodivergent and diastereodivergent transformations can be readily achieved just by the choice of catalyst or modification of reaction conditions. [2] In sharp contrast, reported catalytic enantioselective regiodivergent reactions, especially in an organocatalytic manner, are very limited. [3] To enrich the content of switchable divergent asymmetric synthesis, the development of a new strategy for the target-and diversity-oriented synthesis with high chemo-, regio-and stereodivergence is highly desirable.…”