{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2025,10,11]],"date-time":"2025-10-11T02:21:14Z","timestamp":1760149274213,"version":"build-2065373602"},"reference-count":24,"publisher":"MDPI AG","issue":"15","license":[{"start":{"date-parts":[[2023,7,28]],"date-time":"2023-07-28T00:00:00Z","timestamp":1690502400000},"content-version":"vor","delay-in-days":0,"URL":"https:\/\/creativecommons.org\/licenses\/by\/4.0\/"}],"funder":[{"name":"National Science Foundation","award":["CHE-2102579","FSU075000NMR"],"award-info":[{"award-number":["CHE-2102579","FSU075000NMR"]}]},{"name":"FSU NMR facility","award":["CHE-2102579","FSU075000NMR"],"award-info":[{"award-number":["CHE-2102579","FSU075000NMR"]}]}],"content-domain":{"domain":[],"crossmark-restriction":false},"short-container-title":["Molecules"],"abstract":"<jats:p>We utilized a cycloaromatization reaction driven by relief of excited state antiaromaticity to photouncage aldehydes and ketones. We developed several synthetic routes towards the synthesis of photocaged carbonyls as allylically substituted 3-(2-(arylethynyl)phenyl)prop-2-en-1-ols. A library of photocaged aryl aldehydes and ketones containing donors and acceptors, as well as several photocaged fragrance aldehydes and the steroid 5\u03b1-cholestan- 3 -one, were synthesized and demonstrated photouncaging in good to excellent yields.<\/jats:p>","DOI":"10.3390\/molecules28155704","type":"journal-article","created":{"date-parts":[[2023,7,28]],"date-time":"2023-07-28T02:10:45Z","timestamp":1690510245000},"page":"5704","update-policy":"https:\/\/doi.org\/10.3390\/mdpi_crossmark_policy","source":"Crossref","is-referenced-by-count":2,"title":["Photochemical Uncaging of Aldehydes and Ketones via Photocyclization\/Fragmentation Cascades of Enyne Alcohols: An Unusual Application for a Cycloaromatization Process"],"prefix":"10.3390","volume":"28","author":[{"given":"Adam","family":"Campbell","sequence":"first","affiliation":[{"name":"Department of Chemistry and Biochemistry, Florida State University, Tallahassee, FL 32306, USA"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Nikolas R.","family":"Dos Santos","sequence":"additional","affiliation":[{"name":"Department of Chemistry and Biochemistry, Florida State University, Tallahassee, FL 32306, USA"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-9289-3819","authenticated-orcid":false,"given":"Igor","family":"Alabugin","sequence":"additional","affiliation":[{"name":"Department of Chemistry and Biochemistry, Florida State University, Tallahassee, FL 32306, USA"}],"role":[{"role":"author","vocabulary":"crossref"}]}],"member":"1968","published-online":{"date-parts":[[2023,7,28]]},"reference":[{"key":"ref_1","doi-asserted-by":"crossref","first-page":"3771","DOI":"10.1021\/jo00961a027","article-title":"Phenacyl Photosensitive Blocking Groups","volume":"38","author":"Sheehan","year":"1973","journal-title":"J. Org. Chem."},{"key":"ref_2","doi-asserted-by":"crossref","first-page":"713","DOI":"10.1021\/jo0521551","article-title":"Chain Mechanism in the Photocleavage of Phenacyl and Pyridacyl Esters in the Presence of Hydrogen Donors","volume":"71","year":"2006","journal-title":"J. Org. Chem."},{"key":"ref_3","doi-asserted-by":"crossref","first-page":"6333","DOI":"10.1021\/ja00724a041","article-title":"Photosensitive Protecting Groups","volume":"92","author":"Patchornik","year":"1970","journal-title":"J. Am. Chem. Soc."},{"key":"ref_4","doi-asserted-by":"crossref","first-page":"7170","DOI":"10.1021\/ja00229a036","article-title":"Photolabile 1-(2-Nitrophenyl)Ethyl Phosphate Esters of Adenine Nucleotide Analogs. Synthesis and Mechanism of Photolysis","volume":"110","author":"Walker","year":"1988","journal-title":"J. Am. Chem. Soc."},{"key":"ref_5","doi-asserted-by":"crossref","first-page":"6860","DOI":"10.1021\/ja00334a075","article-title":"Photochemistry of Phosphate Esters: An Efficient Method for the Generation of Electrophiles","volume":"106","author":"Givens","year":"1984","journal-title":"J. Am. Chem. Soc."},{"key":"ref_6","doi-asserted-by":"crossref","first-page":"2723","DOI":"10.1021\/jo0163851","article-title":"A Strategy for the Construction of Caged Diols Using a Photolabile Protecting Group","volume":"67","author":"Lin","year":"2002","journal-title":"J. Org. Chem."},{"key":"ref_7","doi-asserted-by":"crossref","first-page":"697","DOI":"10.1016\/S0040-4039(00)70935-X","article-title":"Photosensitive Protecting Groups","volume":"3","author":"Barltrop","year":"1962","journal-title":"Tetrahedron Lett."},{"key":"ref_8","doi-asserted-by":"crossref","first-page":"6152","DOI":"10.1021\/jo8008275","article-title":"Sequential Removal of Photolabile Protecting Groups for Carbonyls with Controlled Wavelength","volume":"73","author":"Wang","year":"2008","journal-title":"J. Org. Chem."},{"key":"ref_9","doi-asserted-by":"crossref","first-page":"7083","DOI":"10.1021\/acs.orglett.0c02343","article-title":"Antiaromaticity Gain Activates Tropone and Nonbenzenoid Aromatics as Normal-Electron-Demand Diels\u2013Alder Dienes","volume":"22","author":"Karas","year":"2020","journal-title":"Org. Lett."},{"key":"ref_10","doi-asserted-by":"crossref","first-page":"20303","DOI":"10.1073\/pnas.1908516116","article-title":"Excited-State Proton Transfer Relieves Antiaromaticity in Molecules","volume":"116","author":"Wu","year":"2019","journal-title":"Proc. Natl. Acad. Sci. USA"},{"key":"ref_11","doi-asserted-by":"crossref","first-page":"10942","DOI":"10.1021\/jacs.9b13769","article-title":"Impact of Excited-State Antiaromaticity Relief in a Fundamental Benzene Photoreaction Leading to Substituted Bicyclo[3.1.0]Hexenes","volume":"142","author":"Slanina","year":"2020","journal-title":"J. Am. Chem. Soc."},{"unstructured":"Fern\u00e1ndez, I. (2021). Aromaticity\u2014Modern Computational Methods and Applications, Elsevier.","key":"ref_12"},{"key":"ref_13","doi-asserted-by":"crossref","first-page":"3545","DOI":"10.1021\/ol051280w","article-title":"Photochemical Release of Aldehydes from \u03b1-Acetoxy Nitroveratryl Ethers","volume":"7","author":"Bochet","year":"2005","journal-title":"Org. Lett."},{"key":"ref_14","doi-asserted-by":"crossref","first-page":"1828","DOI":"10.1039\/c39850001828","article-title":"O-Nitrobenzyl Alcohol, a Simple and Efficient Reagent for the Photoreversible Protection of Aldehydes and Ketones","volume":"24","author":"Gravel","year":"1985","journal-title":"J. Chem. Soc. Chem. Commun."},{"key":"ref_15","doi-asserted-by":"crossref","first-page":"1533","DOI":"10.1021\/ol070346f","article-title":"Novel Photolabile Protecting Group for Carbonyl Compounds","volume":"9","author":"Wang","year":"2007","journal-title":"Org. Lett."},{"key":"ref_16","doi-asserted-by":"crossref","first-page":"9924","DOI":"10.1021\/jo981697y","article-title":"An Efficient Photo-SET-Induced Cleavage of Dithiane\u2212Carbonyl Adducts and Its Relevance to the Development of Photoremovable Protecting Groups for Ketones and Aldehydes","volume":"63","author":"McHale","year":"1998","journal-title":"J. Org. Chem."},{"key":"ref_17","doi-asserted-by":"crossref","first-page":"15441","DOI":"10.1021\/jacs.5b07448","article-title":"The Missing C1\u2013C5 Cycloaromatization Reaction: Triplet State Antiaromaticity Relief and Self-Terminating Photorelease of Formaldehyde for Synthesis of Fulvenes from Enynes","volume":"137","author":"Mohamed","year":"2015","journal-title":"J. Am. Chem. Soc."},{"key":"ref_18","doi-asserted-by":"crossref","first-page":"4495","DOI":"10.1021\/ja029664u","article-title":"Radical-Anionic Cyclizations of Enediynes:\u2009 Remarkable Effects of Benzannelation and Remote Substituents on Cyclorearomatization Reactions","volume":"125","author":"Alabugin","year":"2003","journal-title":"J. Am. Chem. Soc."},{"key":"ref_19","doi-asserted-by":"crossref","first-page":"4941","DOI":"10.1021\/ja00769a025","article-title":"Quantum Organic Photochemistry. II. Resonance and Aromaticity in the Lowest 3.Pi..Pi.* State of Cyclic Hydrocarbons","volume":"94","author":"Baird","year":"1972","journal-title":"J. Am. Chem. Soc."},{"key":"ref_20","doi-asserted-by":"crossref","first-page":"3733","DOI":"10.1081\/SCC-120025182","article-title":"An Alternative Procedure in the Takai Reaction Using Chromium(III) Chloride Hexahydrate as a Convenient Source of Chromium(II)","volume":"33","author":"Boucard","year":"2003","journal-title":"Synth. Commun."},{"key":"ref_21","doi-asserted-by":"crossref","first-page":"4839","DOI":"10.1016\/S0040-4039(00)78926-X","article-title":"Stereospecific Preparation of Terminal Vinyllithium Derivatives by Br\/Li-Exchange with t-Butyllithium","volume":"17","author":"Neumann","year":"1976","journal-title":"Tetrahedron Lett."},{"key":"ref_22","doi-asserted-by":"crossref","first-page":"2590","DOI":"10.1007\/BF00912549","article-title":"Comparative Reactivity of Alkyl, Vinyl, and Acetylene Derivatives of Aluminum","volume":"18","author":"Palei","year":"1969","journal-title":"Bull. Acad. Sci. USSR Div. Chem. Sci."},{"key":"ref_23","doi-asserted-by":"crossref","first-page":"119","DOI":"10.1021\/cr300177k","article-title":"Photoremovable Protecting Groups in Chemistry and Biology: Reaction Mechanisms and Efficacy","volume":"113","author":"Bochet","year":"2013","journal-title":"Chem. Rev."},{"key":"ref_24","doi-asserted-by":"crossref","first-page":"2505","DOI":"10.1002\/ejoc.201201656","article-title":"How to Lose a Bond in Two Ways: The Diradical\/Zwitterion Dichotomy in Cycloaromatization Reactions","volume":"13","author":"Peterson","year":"2013","journal-title":"Eur. J. Org. 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