Joseph Cs. Jaszberenyi

Hypophosphorous acid and its salts: New reagents for radical chain deoxygenation, dehalogenation and deamination

Abstract Thionocarbonates and xanthates of alcohols, bromides, iodides and isonitriles can be transfromed to the corresponding hydrocarbons with hypophosphorous acid or its salts in radical chain reactions.

An improved radical chain procedure for the deoxygenation of secondary and primary alcohols using diphenylsilane as hydrogen atom donor and triethylborane-air as initiator

Abstract Thiocarbonyl derivatives of secondary alcohols are readily reduced by diphenylsilane in a radical chain process at room temperature using triethylborane-air as an initiator. Primary alcohols react similarly at 80°. Comparison is made with the similar reactivity of tris(trimethylsilyl)silane.

On the mechanism of deoxygenation of secondary alcohols by tin hydride reduction of methyl xanthates and other thiocarbonyl derivatives

Abstract The room temperature deoxygenation of xanthates and thionocarbonates using ( n -Bu) 3 Sn-H — Et 3 B — air has been studied, especially with 119 Sn N.M.R. spectroscopy. The original conception of tin radical attack on thiocarbonyl is confirmed.

The invention of radical reactions. Part XXI. Simple methods for the radical deoxygenation of primary alcohols.

Abstract Novel radical-chain deoxygenations of primary alcohols are described. The alcohols are acylated with the reagents pentafluorophenyl chlorothionoformate, 2,4,6-trichlorophenyl chlorothionoformate and 4-fluorophenyl chlorothionoformate and the intermediate thionocarbonates are deoxygenated with tributyltin hydride, triphenylsilane, diphenylsilane or phenylsilane in high-yielding reactions.

Towards dideoxynucleosides: the silicon approach

Dixanthanes, formed from vic-diols, can easily be transformed to the corresponding olefins with diphenylsilane in a new, high-yielding radical reaction.

The generation and reactivity of oxygen centered radicals from the photolysis of derivatives of N-hydroxy-2-thiopyridone.

Abstract Oxygen centered radicals, formed by the photolysis of derivatives of N -hydroxy-2-thiopyridone, have been trapped by vinyl ethers. In the case of the benzoyloxy radical, smooth deoxygenation is effected by III P compounds. Evidence for the formation of the dimethyl t butylsilyloxy and of the hydroxy radical is also presented.

Ru(bpy)32+-mediated addition of Se-phenyl p-tolueneselenosulfonate to electron rich olefins

The addition of Se-phenyl p-tolueneselenosulfonate 1 to electron rich olefins 4a–4e upon visible light photolysis with a catalytic amount of tris(2,2′-bipyridine)ruthenium(II) gives adducts 5 in high yield.

Radical mono- and dideoxygenations with the triethylsilane + benzoyl peroxide system.

Abstract Thionocarbonates and xanthates of primary and secondary alcohols, as well as dixanthates of vic-diols can easily be deoxygenated to the corresponding hydrocarbons or olefins with triethylsilane and benzoyl peroxide in high-yielding radical reactions.

The invention of radical reactions part xxiii. new reactions nitrile and thiocyanate transfer to carbon radicals from sulfonyl cyanides and sulfonyl isothiocyanates

Abstract Reaction of p-toluenesulphonyl cyanide or methanesulfonyl cyanide with carbon radicals, generated from the corresponding O-acyl-N-hydroxy-2-thiopyridone derivatives by visible light photolysis gives nitriles in good yield. The homolysis products of these sulfonyl nitriles can also be trapped by electron rich olefins. We have also found that carbon radicals react easily with mesyl or tosyl isothiocyanate producing thiocyanates.

Radical deoxygenations and dehalogenations with dialkyl phosphites as hydrogen atom sources

Abstract Thionocarbonates and xanthates of alcohols, and various halides and phenylselenides can be transformed to the corresponding hydrocarbons with alkyl phosphites and benzoyl peroxide in most cases in high-yielding radical reactions.