Photochemistry of S-Phenacyl Xanthates
| Authors | |
|---|---|
| Year of publication | 2011 |
| Type | Article in Periodical |
| Magazine / Source | Journal of Organic Chemistry |
| MU Faculty or unit | |
| Citation | |
| Doi | http://dx.doi.org/10.1021/jo201385b |
| Field | Organic chemistry |
| Keywords | Reversible addition-fragmentation transfer; RAFT; macromolecular design via the interchange of xanthates; MADIX; xanthates; phenacyl compounds; photochemistry; photoremovable protecting groups; laser flash spectroscopy; DFT calculations. |
| Description | Various synthetically readily accessible S-phenacyl xanthates are shown to undergo photoinitiated homolytic scission of the C-S bond in the primary step. The resultant fragments, phenacyl and xanthic acid radicals, recombine to form symmetrical 1,4-diketones and xanthogen disulfides, respectively, in high to moderate chemical yields in chemically inert solvents. They can also be efficiently trapped by a hydrogen-atom donating solvent to give acetophenone and xanthic acid derivatives. The latter compound is in situ thermally converted to the corresponding alcohol in high chemical yields. S-Phenacyl xanthates could thus be utilized as synthetic precursors to the above mentioned compounds, or as photoremovable protecting groups for alcohols, in which the xanthate moiety represents a photolabile linker. The photochemically released phenacyl radical fragments efficiently but reversibly add to the thiocarbonyl group of the parent xanthate molecule. |
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