Selective C–C Bond Cleavage of Cycloalkanones by NaNO₂/HCl

Abstract

A novel selective fragmentation of cycloalkanones by NaNO2/HCl has been established. The C–C bond cleavage reaction proceeds smoothly under mild conditions, selectively affording versatile keto acids or oxime acids. The methodology can streamline the synthesis of valuable chiral molecules and isocoumarins from readily available feedstocks.

Unraveling Precise Locations of Indium Atoms in g‐C3N4 for Ameliorating Hydrogen Peroxide Piezo‐Photogeneration

“…[ 18 ] Additionally, single‐atom sites can help reduce the energy barriers for reactant adsorption and activation processes during catalytic conditions. [ 19 ] However, most research focused on metals from IA to IIB groups, leaving the gap for metals from IIIA to VA due to the present difficulty. A few studies reported using aluminum (Al) and indium (In) to dope into g‐C 3 N 4 lattices to improve photocatalytic activities.…”

Two in one: A Brønsted acid grafted photoactive covalent organic framework as metal-free dual photocatalyst for aerobic oxidative C-C cleavage

“…We were able to isolate the TEMPO-adduct product and analyze it by 1 H NMR (Figure S14), implying a process of carbon radical formation was involved in this oxidative C-C bond cleavage reaction [69]. Finally, according to previous homogeneous catalyst case reports, enol ester and peroxy alcohol are possible intermediates [12,[14][15][70][71]. In order to examine the possible reaction intermediates, an enol ester 4a and a peroxy alcohol 5a were synthesized (For details, please see the Supporting Information).…”

“…This reaction, suitable for various ketone substrates, is catalyzed by an iridium complex combined with an organophosphorus ligand at high temperature [11]. In 2021, Huang et al reported a selective C-C bond cleavage of cycloalkanones using NaNO2 and HCl to produce keto acids or oximes via a nitroso cycloalkanone intermediate [12]. These excellent studies provide inspiration for subsequent research.…”

Palladium/Iron-Catalyzed Wacker-Type Oxidation of Aliphatic Terminal and Internal Alkenes Using O2

“…5-Oxohexanoic Acid (2l). 64 Method B was applied. Purification by silica gel column chromatography (hexane/ ethyl acetate = 1:1) afforded a colorless oil (57 mg, 0.44 mmol, 88% yield).…”