Quinoline-2-sulfoxides, reaction with

Barton devised a new method for the oxidation of primary alcohols to aldehydes involving in the first step conversion to the alkyl chloroformate (1) by adding a solution of the alcohol in ether to ether saturated with phosgene (15-20% w./v.) the solvent is removed at reduced pressure. If the alcohol is hindered, quinoline is added as catalyst and the quinoline hydrochloride removed by filtration. The next step, reaction with dimethyl sulfoxide, is attended with evolution of carbon... 

Radical nucleophile oxidation based on one-electron oxidation, known as the Minisci reaction, is employed for the functionalization of /V-heterocycles with acidic hydrogen peroxide in the presence of iron(II) salts (Figure 3.112).472 A range of A-heterocycles (pyridines, pyrazines, quinolines, etc.) which are activated towards attack by nucleophilic radicals when protonated are suited to this chemistry. The Minisci reaction is suitable for the preparation of carboxylic amides (from formamide), carboxylic esters (from pyruvic esters via a hydroxyhydroperoxide), aldehydes (from 1,3,5-trioxane) and alkylated pyridines (either from carboxylic acids or from alkyl iodides in dimethyl sulfoxide).473 The latter reaction uses dimethyl sulfoxide as the source of methyl radical (Figure 3.112). 

The quinoline dimer (151) became the sole product when the alkyl 2-quinolinylsulfoxide was treated with an alkyl Grignard reagent. The reaction showed a remarkably high reaction rate. In the case of sulfoxide (86), it reached completion in less than 20 seconds at - 78°C, affording a near quantitative yield of the product (151). ... 

Benzyl ethyl sulfide allowed to react with 1,4-diazabicyclo [2.2.2] octane bromine complex in aq. 70%-acetic acid benzyl ethyl sulfoxide. Y 95%. — The reaction is very rapid. The products are completely free from sulfones. Neither cleavage of aliphatic G-S-bonds, which may occur when N-bromosuccinimide is used, nor ar. bromination, when bromine is used, has been observed. F. e., also O-labeled sulfoxides with 0-enriched water, and use of bromine complexes with pyridine and quinoline, s. S. Oae et al.. Bull. Ghem. Soc. Japan 39, 364 (1966). 

Cyclic (hetero- and carbocyclic) vinyl sulfoxides have been prepared by a tandem Michael addition/Homer olefination reaction of a-phosphorylvinyl sulfoxides and carbonyl compounds bearing a nucleophilic center. Using optically active a-phosphorylvinyl sulfoxides a series of enantiomeric cyclic vinyl sulfoxides in which the chiral sulfinyl group is bonded to a chromene, pyrrazolyne, quinoline or cyclopen-tene ring, has been obtained. The H-W-E reaction of aldehydes with sulfinimine-derived 3-oxo pyrrolidine phosphonates (228) represents a new method for the asymmetric synthesis of ring-functionalized cw-2,5-disubstituted 3-oxo pyrrolidines (229) (Scheme 90). ... 

---