Alkenes thiols

Thiol Alkene+H2S (peroxide or UV) (Anti-Markovnikoff addition)... 

Scheme 11.1 Free radical thiol/alkene polymerization [8].

Goldmann et al. [31] introduced azido groups using thiol-alkene method through 1-azido-undecan-l 1-thiol first, then the point-and-click reaction of alkyle functionalized poly-2-hydroxyethanyl acrylate and azido groups to achieve the hydrophilic modification of polydivinylbenzene microspheres. 

Like the 1,3-dipolar Huisgen cycloaddition reaction between azides and acetylenes, thiol-ene chemistry is more than a century old, with the first thiol-alkene addition reaction having been reported by Posner in 1905 [19]. The first thiol-ene... 

This reaction enables the detection of sulfur monoxide and other reduced sulfur compounds that can react with ozone to initially form sulfur monoxide. The chemiluminescence intensity depends on the type of compound, with thiols giving the largest response followed by alkyl sulfides, hydrogen sulfide, and thiophenes. Detection limits in the parts per billion range can be achieved for thiols. Alkenes, which also react with ozone to give emission centered at 354 nm, potentially interfere but selectivity can be achieved with a suitable optical filter. 

Roper TM, Guymon CA, Jonsson ES, Hoyle CE. Influence of the alkene structure on the mechanism and kinetics of thiol-alkene photopolymerizations with real-time infrared spectroscopy. J Polym Sci Part A Polym Chem 2004 42 6283-6298. 

Reactions of Sulphenic Acids.—In continuation of previous work, penicillin sulphenic acids have been trapped with vinyl ethers and keten acetals, " " with thiols, alkenes, and alkynes. A variety of products from thermolysis of N-benzyloxycarbonyl-L-(S-t-butyl)cysteinyl-L-valine methyl ester S-oxide must derive from an intermediate sulphenic acid, and isothiazolones and thiazinones formed from penicillin sulphoxides are also satisfactorily accounted for on the same basis. "... 

Thiol-yne radical reactions follow a similar initiation step to that of thiol-ene reactions. After the initial addition of a thiol to the alkyne and formation of a vinyl radical with a P-thioether function, a hydrogen abstraction from another thiol molecule generates a new thiyl radical. Subsequent addition of a thiyl radical on the vinyl thioether forms another carbon radical, which abstracts a hydrogen from another thiol molecule to give a 1,2-dithioether, and the thiyl radical generated reenters the chain process (Scheme 1.11). The addition of the first thiol to the alkyne is the rate-limiting step, and the second thiol addition to the intermediate thiol-alkene is a faster step. Studies revealed that the second addition is approximately three times faster than the first addition [45]. 

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