Rh-catalyzed regiodivergent hydrosilylation of acyl aminocyclopropanes controlled by monophosphine ligands

Abstract

A Rh-catalyzed regiodivergent hydrosilylation of acyl aminocyclopropanes has been developed.

Design, Synthesis, and Biological Activity of Novel Triazole Sulfonamide Derivatives Containing a Benzylamine Moiety

“…Under a nitrogen atmosphere, cyclopropylamine (1.25 g, 22.0 mmol), N , N ‐diethylethanamine (2.22 g, 22.0 mmol), and hydrofuran (30 mL) were mixed into a 250‐mL flask, stirred at 0°C, and added dropwise with 20 mL of hydrofuran solution of 4 (5.48 g, 20.0 mmol) over 10 min and then eluted with white smoke. The reaction system was reacted at 25°C for 2 h. The mixture was filtered and dried after finishing the reaction to obtain a white solid compound 4.45 g, yield 75% .…”

1,3‐Difunctionalization of Aminocyclopropanes via Dielectrophilic Intermediates

“…[3] Although D-A aminocyclopropanes exhibit excellent reactivity,itusually takes extra steps to remove the electron-withdrawing groups or to transform them into other functionalities.F or simple aminocyclopropanes lacking electron-withdrawing substituents at the vicinal position, current activation strategies focus mainly on:1 )o xidizing the amino group to ar adical cation by strong oxidants or using photoredox chemistry; [4] and 2) utilizing transition-metal catalysts to form metallocyclobutane intermediates. [5] In both cases,the reported transformations were mostly limited to annulations. When considering the importance of 1,3-difunctionalized propylamines in medicinal chemistry,w ith already commercialized drugs such as amprenavir (1)a nd proglumide (2) (Scheme 1B), the development of new synthetic methods starting from aminocyclopropanes appears therefore highly desirable.…”

Cu‐NHC‐Catalyzed Enantioselective Conjugate Silyl addition to Indol‐1‐ylacrylate Derivatives

“…Furthermore, Miura reported a copper‐catalyzed regio‐ and stereoselective aminoboration of vinylsilanes with bis(pinacolato)diboron and hydroxylamines . Recently, Yamaguchi discovered Rh‐catalyzed hydrosilylation of acyl aminocyclopropanes via C–C bond cleavage . Oestrich reported decarboxylative silylation starting from α‐amino acid .…”

“…[9] Recently, Yamaguchi discovered Rh-catalyzed hydrosilylation of acyl aminocyclopropanes via C-C bond cleavage. [10] Oestrich reported decarboxylative silylation starting from α-amino acid. [11] Despite the above certain advances, synthesis of functionalized chiral α-silaneindoles remains virtually unexplored.…”