DMSO作为新的合成子在有机合成中的应用研究进展

二甲亚砜(DMSO)不但可以作为有机溶剂,同时还可以作为反应试剂,在有机合成中得到了广泛的应用.由于其具有来源广、价格低廉、操作简单等优点,近年来将DMSO作为反应试剂应用于有机合成反应引起了广大化学家的关注.本文作者对近几年来DMSO作为合成子在有机合成中的应用按照引入官能团的种类进行了总结,详细阐述了其转化为甲磺酰基、甲酰基、氰基、甲硫基等官能团的方法学研究,以期为开发DMSO新的应用提供参考依据.     

Collection of NMR Scalar and Residual Dipolar Couplings Using a Single Experiment

A new DMSO‐compatible aligning gel based on cross‐linked poly(2‐hydroxylethyl methacrylate) (poly‐HEMA) has been developed. Due to a significant difference in bulk magnetic susceptibility between the DMSO inside and outside the gel, it is possible to simultaneously collect isotropic and anisotropic NMR data, such as residual dipolar couplings (RDC), in the same NMR tube. RDC‐assisted structural analysis of menthol and the alkaloid retrorsine is reported as proof of concept.     

I2–DMSO promoted intramolecular oxidative cyclization of 2-(aryl or alkyl amino)-acetophenones for the synthesis of isatins

An I₂–DMSO promoted novel and efficient method is described for the synthesis of isatins from 2-aminoaryl methyl ketone. A series of alkyl or aryl isatin derivatives were successfully synthesized under the optimized reaction conditions.     

Novel and Efficient Oxidation of Benzyl Ethers to Benzaldehydes by DMSO/49% Aq. HBr

Dimethylsulfoxide (DMSO) oxidizes benzyl ethers into corresponding benzaldehydes at 110°C; the reaction is accelerated by 49% aq. HBr. The conditions work well for different aryl‐substituted benzyl ethers. This protocol is inert toward dialkyl ethers.     

Synthesis of 10-Hydroxycamptothecin: Evaluation of New Moderators for the Chemoselective Reduction of Camptothecin

Abstract

10-Hydroxycamptothecin is prepared by chemoselective catalytic hydrogenation of the B-ring of camptothecin over PtO₂ with sulfur moderators followed by oxidation using iodobenzenediacetate. New moderators (viz. thioanisole, dimethyl sulfide, diphenyl sulfide, 2-mercapto ethanol), which moderate the hydrogenation of the B- ring of camptothecin, are being explored.

DMSO-Enabled Selective Radical O−H Activation of 1,3(4)-Diols

Control of selectivity is one of the central topics in organic chemistry. Although unprecedented alkoxyl-radical-induced transformations have drawn a lot of attention, compared to selective C−H activation, selective radical O−H activation remains less explored. Herein, we report a novel selective radical O−H activation strategy of diols by combining spatial effects with proton-coupled electron transfer (PCET). It was found that DMSO is an essential reagent that enables the regioselective transformation of diols. Mechanistic studies indicated the existence of the alkoxyl radical and the selective interaction between DMSO and hydroxyl groups. Moreover, the distal C−C cleavage was realized by this selective alkoxyl-radical-initiation protocol.     

Synthesis of quinazolinones from anthranilamides and aldehydes via metal-free aerobic oxidation in DMSO

A highly environmentally benign protocol for the synthesis of quinazolinones from anthranilamides and aldehydes via aerobic oxidation was developed in wet DMSO. This protocol is operationally simple, exhibits broad substrate scope, and does not need toxic metal catalysts and bases. In addition, the utility of this transformation was further demonstrated by converting the resulting quinazolinones into other useful products in the same-pot without their isolation.     

Synthesis, spectroscopic characterization, DFT studies and biological assays of a novel gold(I) complex with 2-mercaptothiazoline

A new gold(I) complex with 2-mercaptothiazoline (MTZ) with the coordination formula [AuCN(C₃H₅NS₂)] was synthesized and characterized by chemical and spectroscopic measurements, DFT studies and biological assays. Infrared (IR) and ¹H, ¹³C and ¹⁵N nuclear magnetic resonance (NMR) spectroscopic measurements indicate coordination of the ligand to gold(I) through the nitrogen atom. Studies based on DFT confirmed nitrogen coordination to gold(I) as a minimum of the potential energy surface with calculations of the hessians showing no imaginary frequencies. Thermal decomposition starts at temperatures near 160 °C, leading to the formation of Au⁰ as the final residue at 1000 °C. The gold(I) complex with 2-mercaptothiazoline (Au-MTZ) is soluble in dimethyl sulfoxide (DMSO), and is insoluble in water, methanol, ethanol, acetonitrile and hexane. The antibacterial activities of the Au-MTZ complex were evaluated by an antibiogram assay using the disc diffusion method. The compound showed an effective antibacterial activity against Staphylococcus aureus (Gram-positive) and Escherichia coli and Pseudomonas aeruginosa (Gram-negative) bacterial cells. Biological analysis for evaluation of the cytotoxic effect of the Au-MTZ complex was performed using HeLa cells derived from human cervical adenocarcinoma. The complex presented a potent cytotoxic activity, inducing 85% of cell death at a concentration of 2.0 μmol L⁻¹.     

Synthesis of Aromatic Aldehydes by a Fast Method Involving Kornblum's Reaction

Aromatic aldehydes were synthesized by oxidation of corresponding halides with dimethyl sulfoxide on potassium bicarbonate by microwave irradiation. Short reaction time and high yields were obtained.