Visible-Light-Induced Enantioselective Dearomative [2+2]-Cycloaddition/Ring-Expansion Sequence of Indoles with Simple Alkenes DOI
Xiaohua Liu, Weidi Cao, Xiaoming Feng

et al.

Synlett, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 28, 2025

Abstract Catalytic asymmetric dearomatization reactions represent a versatile platform for constructing complex optically active three-dimensional molecules. We present visible-light-induced dearomative [2+2] cycloaddition/ring-expansion reaction of indole derivatives with simple alkenes in the presence chiral N,N′-dioxide/terbium complex. This strategy provides access to range valuable cyclopenta[b]indoles, and its synthetic potential is further showcased through gram-scale synthesis, bioactivity against human breast cancer, transformation into yuehchukene analogue. A series control spectral experiments, as well DFT calculations, provide compelling evidence elucidate mechanism.

Language: Английский

Iron-Catalyzed Asymmetric Imidation of Sulfides via Sterically Biased Nitrene Transfer DOI
Zhenzhong Liu, Hongli Wu,

H Huiqi Zhang

et al.

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(26), P. 18050 - 18060

Published: June 15, 2024

Transition-metal-catalyzed enantioselective nitrene transfer to sulfides has emerged as one of the most powerful strategies for rapid construction enantioenriched sulfimides. However, achieving stereocontrol over highly active earth-abundant transition-metal nitrenoid intermediates remains a formidable challenge compared with precious metals. Herein, we disclose chiral iron(II)/N,N′-dioxide-catalyzed imidation dialkyl and alkyl aryl using iminoiodinanes precursors. A series sulfimides were obtained in moderate-to-good yields high enantioselectivities (56 examples, up 99% yield, 98:2 e.r.). The utility this methodology was demonstrated by late-stage modification complex molecules synthesis insecticide sulfoxaflor related bioactive compounds. Based on experimental studies theoretical calculations, water-bonded high-spin iron species identified key intermediate. observed stereoselectivity original from steric repulsion between amide unit ligand cave bulky substituent sulfides. Additionally, dioxazolones proved be suitable acylnitrene precursors presence an iron(III)/N,N′-dioxide complex, resulting formation enantioselectivity-reversed (14 81% 97:3

Language: Английский

Citations

11
Visible-Light-Induced Enantioselective Dearomative [2+2]-Cycloaddition/Ring-Expansion Sequence of Indoles with Simple Alkenes DOI
Xiaohua Liu, Weidi Cao, Xiaoming Feng

et al.

Synlett, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 28, 2025

Abstract Catalytic asymmetric dearomatization reactions represent a versatile platform for constructing complex optically active three-dimensional molecules. We present visible-light-induced dearomative [2+2] cycloaddition/ring-expansion reaction of indole derivatives with simple alkenes in the presence chiral N,N′-dioxide/terbium complex. This strategy provides access to range valuable cyclopenta[b]indoles, and its synthetic potential is further showcased through gram-scale synthesis, bioactivity against human breast cancer, transformation into yuehchukene analogue. A series control spectral experiments, as well DFT calculations, provide compelling evidence elucidate mechanism.

Language: Английский

Citations

0