PhSH reaction with

The 4-chloro-2-nitrobenzyl group was useful in the synthesis of dithymidine phosphorothioates. It could be cleaved with a minimun of side reactions with PhSH, TEA. Pyr. ... 

The reaction of thiolate ligands with [Ni(terpy)Cl2] in MeOH or MeCN affords different products depending on the basicity and bulk of the thiolate ligand employed. Thus, the reaction with PhSH yields the thiolate bridged dimer [Ni(terpy)(SPh)2]2-6CH3OH (281), reaction with C6F5SH yields the... 

Ono and coworkers have extended the radical elimination of v/c-dinitro compounds to P-nitro sulfones151 and P-nitro sulfides.138,152 As P-nitro sulfides are readily prepared by the Michael addition of thiols to nitroalkenes, radical elimination of P-nitrosulfides provides a useful method for olefin synthesis. For example, cyclohexanone is converted into allyl alcohol by the reaction shown in Eq. 7.110. Treatment of cyclohexanone with a mixture of nitromethane, PhSH, 35%-HCHO, TMG (0.1 equiv) in acetonitrile gives ahydroxymethylated-P-nitro sulfide in 68% yield, which is converted into the corresponding allyl alcohol in 86% yield by the reaction with Bu3SnH.138 Nitro-aldol and the Michael addition reactions take place sequentially to give the required P-nitro sulfides in one pot. 

Cyclizations of amidyl radicals have been studied both synthetically and kinetically. A detailed study on the rates of a variety of amidyl radical reactions was determined by both LFP and indirect competition methods (Table l) In addition, the rate constants for reactions with BusSnH and PhSH were also reported (thus giving a range of simple amidyl radical clocks). The results obtained will be useful in synthetic sequenceplanning involving amidyl radicals. 

It is not surprising that chloro esters 1, 2 readily add thiols, catalyzed by sodium thiolates or triethylamine, to give the corresponding 2-(r-organylthiocy-clopropyl)-2-chloroacetates 85,86 (Scheme 22) [15 b, 22b, 27]. This reaction with thiophenol has been used to quantify the Michael reactivity of 1-Me, 2-Me, 3-X in comparison to simple acrylates (see above). With an excess of PhSH, the nucleophilic substitution of the chlorine in 85 a (but not in 85h) proceeded to give the corresponding bis(phenylthio) derivative in 63% yield [15bj. Alkali thiolates (e.g. NaSMe, NaSBn) add smoothly onto 1-Me, 2c-Me and 2p-Me at - 78 °C, because at this temperature subsequent nucleophilic substitution of the chlorine is much slower [7l, 9]. The Michael additions of sodium phenylselenide and sodium arylsulfenates onto 1-Me and their synthetic utility have been discussed above (see Table 1). 

Reaction of the methoxo complex 162 with PhSH gave the thiolate complex 168, while reaction with the weak carbon acid PhC = Cl I, gave the corresponding al-kynyl complex 169.74 Reaction of 114 with Tl(acac) gave the C-bonded acac complex 170, which exists as a mixture of tautomers. 

The presence of radical intermediates was supported by observation of the ESR signal for a mixture of 360 and PhSH in DMF. On the other hand, the reaction with MeONa to give 361a may involve an addition of the nucleophile followed by elimination of chloride ions. 

It should be pointed out that in nucleophilic reactions, where the second step is protonation, as well as in the capture of the carbocation formed in the course of electrophilic reactions with bicyclobutane, the reactive intermediates are preferentially trapped from an equatorial direction. A priori, there is no obvious stereoelectronic driving force for this exceptional behavior of the reaction of PhSH with 60. However, in this specific case, it could stem from a steric repulsion between the methylene group at position 4 of the tricyclic system and the phenyl group of the PhS either entering or already present. Supporting this assumption are reactions of thiyl radical with bicyclobutane (equation 85) " . In the absence of the steric effects of the tricyclic system, the cis and trans isomers were obtained in equal amounts. Hence, at this stage, it seems that unlike the reactions of cyclobutyl carbanion or carbocation, stereoselectivity in the trapping radical... 

Removal of the ester Et group with Me SiBr, followed by treatment of the product (112 d) with oxalyl chloride led to the cyclic phosphonic chloride (112 e) as stereoisomeric mixture further reaction with PhSH under basic conditions gave (112 f), also as a mixture of stereoisomers. The (2 ) form of (112 f) reacted with vinylmagnesium bromide to give the 2-vinyl derivative, a step which failed, however, with the (2B) epimer. Attempts to oxidatively cleave the vinyl group and so generate a compound having a carbonyl... 

Oxidative cyclization. Alkynyllactams cycUze by reaction with PhSH and AIBN,... 

CFs when hydrogenated in controlled fashion in the presence of Pd/C, gives a 1 1 adduct with PhSH in the presence of PhSNa, and readily partakes in thermal Diels-Alder reactions with cyclopentadiene, cyclohexa-1,3-diene, 1,3-diphenyliso-benzofuran, and tetraphenylcyclopentadienone (the last is converted into-PhsCe SOs-CFs at 174°C) it reacts 1.7 times faster with cyclopentadiene in ethyl acetate at room temperature than does dimethyl acetylenedicarboxylate. ... 

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