Hydroxymethylaniline Photocages for Carboxylic Acids and Alcohols
| dc.contributor.author | Skalamera, Dani | |
| dc.contributor.author | Bregovic, Vesna Blazek | |
| dc.contributor.author | Antol, Ivana | |
| dc.contributor.author | Bohne, Cornelia | |
| dc.contributor.author | Basaric, Nikola | |
| dc.date.accessioned | 2020-08-21T23:44:27Z | |
| dc.date.available | 2020-08-21T23:44:27Z | |
| dc.date.copyright | 2017 | en_US |
| dc.date.issued | 2017 | |
| dc.description.abstract | ortho-, meta- and para-Hydroxymethylaniline methyl ethers 3–5-OMe and acetyl derivatives 3–5-OAc were investigated as potential photocages for alcohols and carboxylic acids, respectively. The measurements of photohydrolysis efficiency showed that the decaging from ortho- and meta-derivatives takes place efficiently in aqueous solution, but not for the para-derivatives. Contrary to previous reports, we show that the meta-derivatives are better photocages for alcohols, whereas ortho-derivatives are better protective groups for carboxylic acids. The observed differences were fully disclosed by mechanistic studies involving fluorescence measurements and laser flash photolysis (LFP). Photoheterolysis for the para-derivatives does not take place, whereas both meta- and ortho-derivatives undergo heterolysis and afford the corresponding carbocations 3-C and 4-C. The ortho-carbocation 4-o-C was detected by LFP in aqueous solution (λmax = 410 nm, τ ≈ 90 μs). Moreover, spectroscopic measurements for the meta-acetyl derivative 3-m-OAC indicated the formation of cation in the excited state. The application of an ortho-aniline derivative as a protective group was demonstrated by synthesizing several derivatives of carboxylic acids. In all cases, the photochemical deprotection was accomplished in high yields (>80%). This mechanistic study fully rationalized the photochemistry of aniline photocages which is important for the design of new photocages and has potential for synthetic, biological, and medicinal applications. | en_US |
| dc.description.reviewstatus | Reviewed | en_US |
| dc.description.scholarlevel | Faculty | en_US |
| dc.description.sponsorship | These materials are based on work financed by the Croatian Academy of Sciences (HAZU), Croatian Science Foundation (HRZZ IP-2014-09-6312), the Natural Sciences and Engineering Research Council of Canada (NSERC- RGPIN-121389-2012), and the University of Victoria (UVIC). | en_US |
| dc.identifier.citation | Skalamera, D., Bregovic, V. B., Antol, I., Bohne, C., & Basaric, N. (2017). Hydroxymethylaniline Photocages for Carboxylic Acids and Alcohols. Journal of Organic Chemistry, 82(23), 12554-12568. https://doi.org/10.1021/acs.joc.7b02314. | en_US |
| dc.identifier.uri | https://doi.org/10.1021/acs.joc.7b02314 | |
| dc.identifier.uri | http://hdl.handle.net/1828/12011 | |
| dc.language.iso | en | en_US |
| dc.publisher | Journal of Organic Chemistry | en_US |
| dc.subject | Alcohols | |
| dc.subject | Solution chemistry | |
| dc.subject | Reaction products | |
| dc.subject | Fluorescence | |
| dc.subject | Cations | |
| dc.subject.department | Department of Chemistry | |
| dc.title | Hydroxymethylaniline Photocages for Carboxylic Acids and Alcohols | en_US |
| dc.type | Postprint | en_US |