From thiols

Al-Obaidi A H R, Rigby S J, Hegarty J N M, Bell S E J and McGarvey J J 1996 Direct formation of silver and gold metal liquid-like films (MELLFS) from thiols and sols without organic solvents SERS and AFM studies ICORS 96 XVth Int. Conf on Raman Spectroscopy ed S A Asher and P B Stein (New York Wiley) pp 590-1... 

Disulfide(s), 668 from thiols, 668 hybridization of, 20 reduction of, 668 thiols from. 668... 

Dithiols and dienes may react spontaneously to afford dithiols or dienes depending on the monomer dithiol ratio.221 However, the precise mechanism of radical formation is not known. More commonly, pholoinilialion or conventional radical initiators are employed. The initiation process requires formation of a radical to abstract from thiol or add to the diene then propagation can occur according to the steps shown in Scheme 7.17 until termination occurs by radical-radical reaction. Termination is usually written as involving the monomer-derived radicals. The process is remarkably tolerant of oxygen and impurities. The kinetics of the tbiol-ene photopolymerizalion have been studied by Bowman and... 

A1BN, iw azobisisnbutyronilrile aldehydes, acyl radicals from 1 18 alkanelhiyl radicals Irom ally] sulfides 300 from disunities 291-2 from thiols 290, 291 polarity 290... 

The low reactivity of alkyl and/or phenyl substituted organosilanes in reduction processes can be ameliorated in the presence of a catalytic amount of alkanethiols. The reaction mechanism is reported in Scheme 5 and shows that alkyl radicals abstract hydrogen from thiols and the resulting thiyl radical abstracts hydrogen from the silane. This procedure, which was coined polarity-reversal catalysis, has been applied to dehalogenation, deoxygenation, and desulfurization reactions.For example, 1-bromoadamantane is quantitatively reduced with 2 equiv of triethylsilane in the presence of a catalytic amount of ferf-dodecanethiol. 

Answer Friedel-Crafts disconnection reveals 1,2-diX compound (21) easily made from thiol (22) and chloro-acetic acid. Thiol (22) can be made by the thiourea route (p T 37 ). 

The reagent (1) is easily made from thiol (3) and ethylene oxide or 2-chloroethanol (2). The acid RCOgH is then protected by acid-catalysed ester (4) formation. 

Anions derived from thiols are strong nucleophiles and are easily alkylated by halides. 

The asymmetric reduction of the benzoxathiin is very appealing because of its simplicity (Scheme 5.3). It was envisioned that intermediate 16 could be prepared from thiol-phenol 7 and bro moke tone 17. Scheme 5.8 summarized the synthesis for 16. The l,3-benzoxathiol-2-one 35 was prepared from 1,4-benzoquinone and thiourea following a literature procedure with minor modifications. Benzylation of 35 with benzyl bromide in the presence of KI gave benzyl ether 36 as a crystalline solid. It was observed that the benzylation gave better results when the reaction was run under anaerobic conditions. Hydrolysis of thiocarbonate 36 gave free thiophenol 7 which was used directly in the next reaction. 

It is supposed that the nickel enolate intermediate 157 reacts with electrophiles rather than with protons. The successful use of trimethylsilyl-sub-stituted amines (Scheme 57) permits a new carbon-carbon bond to be formed between 157 and electrophiles such as benzaldehyde and ethyl acrylate. The adduct 158 is obtained stereoselectively only by mixing nickel tetracarbonyl, the gem-dibromocyclopropane 150, dimethyl (trimethylsilyl) amine, and an electrophile [82]. gem-Functionalization on a cyclopropane ring carbon atom is attained in this four-component coupling reaction. Phenyl trimethyl silylsulfide serves as an excellent nucleophile to yield the thiol ester, which is in sharp contrast to the formation of a complicated product mixture starting from thiols instead of the silylsulfide [81]. (Scheme 58)... 

Form sulfide from thiol (NaOH, R CH2X)... 

This synthesis demonstrated that the neighboring-group participation effect on the stereoselectivity of glycosylation reactions can be extended to sohd-phase processes. In this case, milder and more practical cleavage conditions than previously discussed were established. The use of /V- bromosuccinimide as the thiophilic reagent in acetone/water or tetrahydrofuran/methanol permitted the release of oligosaccharides in form of lactols or 1-0-Me glycosides, respectively. The tetrasaccharide derivative was isolated in 34% yield from thiol resin 3 (80% yield per step). 

Unsymmetrical and symmetrical dialky trithiocarbonates from thiols... 

Figure 6.10 Equilibration of dynamic thiolester libraries ( ) DCL-A from thiol 1 and thiolesters 16-20 (T) DCL-B from thiol (1) and thiolesters 16-18, 21, and 22 (modified from Reference 2).

Formation of SAMs from Thiol Compounds on Gold Surfaces. 39... 

DESULFURIZATION WITH RANEY NICKEL Preparation of Aldehydes from Thiol Esters [1101]... 

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