Catalytic Enantioselective Alkene Aminohalogenation/Cyclization Involving Atom Transfer

Abstract

Problem solved: The title reaction was used for the synthesis of chiral 2‐bromo, chloro, and iodomethyl indolines and 2‐iodomethyl pyrrolidines (see scheme). Stereocenter formation is believed to occur by enantioselective cis aminocupration and CX bond formation is believed to occur by atom transfer. The ultility of the products as versatile synthetic intermediates was demonstrated, as was a radical cascade cyclization sequence.

Metal Carbides as Alternative Electrocatalyst Supports

“…While the majority of the methods involve the intermediacy of electrophilic chiral halonium ions, 51 alternative methods involving chiral nucleophilic intermediates 52 and halogen-atom transfer to chiral β-amino-radical intermediates 53 have also been reported. As the utility of chiral vicinal aminohalides is likely to be high, it is expected the number of contributions in this area will continue to grow.…”

“…53 The reaction is catalyzed by [Cu( R,R )-Ph-box](OTf) 2 (20 mol %) and isopropyl iodide is the source of halogen atom.…”

Cu‐Catalyzed Heterocycle Synthesis

“…A range of chiral 2-iodomethyl indolines and pyrrolidines could be formed in good to excellent yield and enantioselectivity. In addition, 1,1-dichloroethene and (2,2-dibromo-1-methylcyclopropyl)benzene also could lead to aminochloride and aminobromide products in moderate yield and good enantioselectivity [61] (Scheme 8.25).…”

Amidato complexes of ruthenium, rhodium and iridium from concise N–H bond activation: exploration in catalysis

“…methylbenzenesulfonamide19 (391 mg, 1.0 mmol) was dissolved in 5 mL of freshly distilled dichloromethane. Grubbs-Hoveyda catalyst (19 mg, 0.03 mmol) and methyl acrylate (0.8 mL, 9.0 mmol) were subsequently added in single portions and the reaction was refluxed for 18 h at 50 C (external oil bath temperature).…”