In this doctoral thesis, we have studied the oxidation of carboxylic acids to obtain the corresponding acyloxy radicals, using visible light and non-toxic and inexpensive organic dyes, as photocatalysts. On the one hand, we study the photooxidation of aromatic carboxylic acids to obtain acyloxy radicals, whose decarboxylation is relatively slow (Chapter I and Chapter II). On the other hand, we describe the photooxidation of aliphatic carboxylic acids, to take advantage of the rapid decarboxylation of the corresponding acyloxy radicals, to generate nucleophilic radicals that were trapped by different reagents (Chapter III to Chapter V). It should be noted that all the protocols are free of expensive and toxic noble metals, the reactions were promoted with visible light at room temperature and the scalability of some reactions was demonstrated in batch conditions or using flow chemistry. In addition, mechanistic studies were carried out to propose plausible photocatalytic routes to all the reactions studied.

Nitrogen is a vital element for the existence of life, as shown by its frequent presence in essential biomolecules, and inclusion into valuable drugs. Sulfonamides and their heterocycle counterpart, sultams, are N-containing functional groups and metabolically stable amide isosteres. Sulfa drugs, which contain these moieties, have a broad spectrum of medical applications. The industrial value of sultams has prompted the development of novel methods for their synthesis, and metal-catalyzed C-H amination reactions with nitrene precursors have recently shown promise. The current thesis presents a survey of conditions for benzo[d]sultam synthesis via intramolecular C-H amination of N-acyloxysulfonamides. Initially, using Ru(Bpy)3(PF6)2 as a photocatalyst and Et3N as a base enabled benzo[d]sultam formation by tertiary C-H amidation. The photoredox conditions were optimized to accommodate other 2,6-disubstituted-N-acyloxysulfonamides upon omission of the base, which consistently gave sulfonamide byproducts. Control reactions indicated that a thermal base-induced reaction was simultaneously occurring, both enabling productive C-H amidation and byproduct formation. Systematic optimization of base-induced conditions enabled sultam synthesis from 2,6-dialkyl- and tertiary ortho-monoalkyl-precursors in moderate yield, but sulfonamide formation still impeded the reaction.   An additional control reaction indicated that a thermal Ruthenium-catalyzed C-H amidation reaction was possible. Indeed, heating N-acyloxysulfonamides in the presence of Ru(Bpy)3(PF6)2 and in the absence of light and base enabled efficient C-H amidation, particularly with DCE as a solvent. A representative scope of 12 benzo[d]sultams was then synthesized including entries derived from ortho-monoalkyl-N-acyloxyarylsulfonamides. Aside from optimizing an efficient reaction for the synthesis of benzo[d]sultams through the cyclization of N-acyloxyarylsulfonamides, including the challenging primary C-H amidation of orthomonomethyl-substrates, the unique reaction conditions developed in this thesis set precedent for future investigation of hydroxylamine derived nitrene precursors. The optimization and design of superior ruthenium catalysts could allow for more challenging C-H amination reactions with hydroxysulfonamide derivatives and similar N-oxy nitrene precursors.

京都大学 / 新制・課程博士 / 博士(工学) / 甲第23925号 / 工博第5012号 / 新制||工||1782(附属図書館) / 京都大学大学院工学研究科合成・生物化学専攻 / (主査)教授 村上 正浩, 教授 杉野目 道紀, 教授 中尾 佳亮 / 学位規則第4条第1項該当 / Doctor of Philosophy (Engineering) / Kyoto University / DFAM

En las últimas décadas, los procesos redox fotoinducidos mediados por luz visible han recibido gran atención debido a las suaves condiciones de operación en que se llevan a cabo. Como resultado, se han logrado posicionar como una alternativa más dentro de los Procesos de Oxidación Avanzada. Además, se han convertido en una metodología excepcional en síntesis orgánica, que ha abierto la puerta a nuevas rutas químicas con aplicaciones sintéticas. Sin embargo, a pesar del crecimiento del campo, se ha prestado poca atención a los mecanismos por los que operan estos procesos. El principal objetivo de esta tesis fue avanzar en la comprensión de distintos procesos fotoredox llevados a cabo empleando fotocatalizadores orgánicos. Más específicamente, se estudió la viabilidad de distintos fotocatalizadores orgánicos, y además, se realizó un estudio mecanístico detallado basado en técnicas resueltas en el tiempo. A partir de estos resultados, se estableció una metodología para determinar los puntos clave a considerar en un sistema fotoredox. En primer lugar, en la Parte I, se eligieron dos fotocatalizadores basados en sales de pirilio y tiapirilio, que operan mediante transferencia electrónica oxidativa, con distintos objetivos. En el Capítulo 3, se evaluó su aplicabilidad en la fotodegradación de dos contaminantes de la industria del corcho y se estudió el mecanismo por el que se produce dicha fotodegradación. En el Capítulo 4, se demostró la utilidad de la detección directa de todos los intermedios de vida corta derivados del TPP+ implicados en la oxidación fotocatalizada como herramienta para evaluar el nivel de fotodegradación. En el Capítulo 5, se empleó TPTP+ para establecer las mejores características de un fotocatalizador y la influencia de la concentración de las sustancias a oxidar en la eficiencia de los estados excitados, o en general, de los intermedios clave de vida corta. En segundo lugar, en la Parte II, en el Capítulo 6, se evaluó el potencial del Rosa Bengala en la eliminación de dos fármacos. Éste es un fotocatalizador típico en la remediación de aguas residuales conocido por actuar via mecanismo Tipo II. Se incluyó además un segundo fotocatalizador, Perinaftenona, cuyo rendimiento cuántico de oxígeno singlete es incluso mayor a Rosa Bengala. En el Capítulo 7, se llevó a cabo la fotooxidación de tres contaminantes, usando NMQ+, un fotocatalizador inusual, capaz de generar oxígeno singlete desde su estado excitado singlete. En todos los casos se pudo demostrar la mayor contribución del mecanismo Tipo I sobre el mecanismo Tipo II en la fotodegradación de los diferentes contaminantes. Finalmente, en la Parte II, el Capítulo 8 se dedicó a la reducción fotocatalítica de bromuros orgánicos, empleando Riboflavina, un colorante orgánico no metálico, como fotocatalizador. De nuevo, se prestó especial atención a la detección y comportamiento de las especies intermedias, lo que resultó de acuerdo a los datos termodinámicos. / En les últimes dècades, els processos redox fotoinduïts mitjan per llum visible han rebut gran atenció degut a les suaus condicions d'operació en que es donen. Com a resultat, s'han aconseguit col·locar com una alternativa mes dins dels Processos d'Oxidació Avançada. A més, han estat convertint-se en una metodologia excepcional en síntesi orgànica, que ha obert la porta a noves rutes químiques amb aplicacions sintètiques. No obstant això, a pesar del creixement del camp, s'ha prestat poca atenció als mecanismes pels que operen aquests processos. El principal objectiu d'esta tesi va ser avançar en la comprensió de diferents processos fotoredox duts a terme emprant fotocatalitzadors orgànics. Més específicament, es va estudiar la viabilitat de distints fotocatalitzadors orgànics, i a més, es va realitzar un estudi mecanístic al detall basat en tècniques resoltes en el temps. Amb aquests resultats, es va establir una metodologia per a determinar els punts clau a considerar en un sistema fotoredox. En primer lloc, en la Part I, es van elegir dos fotocatalitzadors basats en sals de pirili i tiapirili, els quals operen per mitjà de transferència electrònica oxidativa, amb distints objectius. En el Capítol 3, es va avaluar la seua aplicabilitat en la fotodegradació de dos contaminants de la indústria del suro i es va estudiar el mecanisme pel qual es produeix dita fotodegradació. En el Capítol 4, es va demostrar la utilitat de la detecció directa de tots els intermedis de curt temps de vida derivats del TPP+ implicats en l'oxidació fotocatalitzada com a ferramenta per avaluar el nivell de fotodegradació. En el Capítol 5, es va emprar TPTP+ per a establir les millors característiques d'un fotocatalitzador i l'influencia de la concentració de les substàncies a oxidar en la eficiència dels estats oxidats, o en general, del intermedis claus de vida curta. En segon lloc, en la Part II, en el Capítol 6, es va avaluar el potencial del Rosa Bengala en l'eliminació de dos fàrmacs. Aquest es un fotocatalitzador típic en la remediació d'aigües residuals conegut per actuar via mecanisme Tipus II. Es va incloure a més un segon fotocatalitzador, Perinaftenona, el del qual rendiment quàntic d'oxigen singlet és inclús major a Rosa Bengala. En el Capítol 7, es va dur a terme la fotooxidació de tres contaminants, usant NMQ+, un fotocatalitzador inusual, capaç de generar oxigen singlet des del seu estat excitat singlet. En tots els casos es va poder demostrar la major contribució del mecanisme Tipus I sobre el mecanisme Tipo II en la fotodegradació dels diferents contaminants. Finalment, en la Part II, el Capítol 8 es va dedicar a la reducció fotocatalítica de bromurs orgànics, emprant Riboflavina, un colorant orgànic no metàl·lic, com fotocatalitzador. De nou, es va prestar especial atenció a la detecció i comportament de les espècies intermèdies, el que va resultar d'acord amb les dades termodinàmiques. / In the last decades, photoinduced-redox processes mediated through visible light have obtained great attention due to the generally mild operating conditions that they offer. As a result, they constitute a further alternative within the so-called Advanced Oxidation processes. Besides, they are becoming an outstanding methodology in organic synthesis, which has opened the door to new synthetic and chemical routes. However, despite the growth of the field, little attention has been paid to the mechanisms pathways behind these processes. The main objective of this thesis was to gain deeper understanding of different photoredox processes carried out using organic photocatalysts. More specifically, the viability of several organic photocatalysts was studied, and besides, a careful mechanistic study based on time resolved techniques supported the postulated mechanisms. With this information, a methodology determining the key points to consider in a photoredox system were stablished. Firstly, in Part I, two photocatalysts based on pyrilium and thiapyrilium salts, which operate through an oxidative electron transfer, have been used with different objectives. In Chapter 3, the viability of the photodegradation of two common pollutants from cork industry and the mechanism behind it has been evaluated. In Chapter 4, the direct detection of all the TPP+ derived short-lived intermediates in the photocatalyzed oxidation of a mixture of pollutants using TPP+ was proposed as a methodology to assess the photodegradation extent. In the last chapter of Part I, Chapter 5, TPTP+ is used to stablish the best characteristics of a photocatalyst. Besides, the study claimed the influence of the concentration of the target substances in the efficiency of the excited states or, in general, of the key short-lived intermediates. Secondly, in Part II, in Chapter 6, Rose Bengal, a typical photocatalyst used in wastewater remediation, known for working via Type II mechanism, was evaluated for the removal of two common drugs. In addition, a second one, Perinaphtenone, which exhibits even a higher singlet oxygen quantum yield than Rose Bengal was tested. In Chapter 7, NMQ+, a non-typical photocatalyst able of generate singlet oxygen from its singlet excited state, was used in the photooxidation of three different pollutants. In every case, the major contribution of Type I vs Type II mechanism was demonstrated. Finally, in Part III, Chapter 8 was devoted to the photocatalytic reduction of organic bromides. In this case, Riboflavine, a non-metallic organic dye, was used as a photocatalyst. Analogously, careful attention was paid to the behavoiur of the intermediates, which were in agreement, as well as to the thermodynamics of the steps involved in the photocatalytic cycle. / Martínez Haya, R. (2018). Photoredox catalysis for environmental and chemical applications. A mechanistically-based approach [Tesis doctoral]. Universitat Politècnica de València. https://doi.org/10.4995/Thesis/10251/114828

The aim of my Ph.D. thesis is to summarize my research on the development of ring-opening polymerization (ROP) of O-carboxyanhydrides (OCAs) to synthesize functionalized, degradable polyesters. Biodegradable polyesters are promising alternatives to conventional petroleum-based non-degradable polyolefins and they are widely used in everyday applications ranging from clothing and packaging to agriculture and biomedicine. Commercially available polyesters, such as poly(lactic-co-glycolic acid), poly(lactic acid), and polycaprolactone, hydrolyze in physicochemical media. They have been approved by FDA and widely used for medical applications. However, the lack of side-chain functionality in polyesters and in corresponding monomers greatly plagues their utility for applications that demand physicochemical properties such as high stiffness, tensile strength and elasticity. Increasing efforts have been devoted to the introduction of pendant groups along the polymer chain in order to modify and modulate the physicochemical properties of polyesters and thereby to expand their applications. Over the last decade, OCAs have emerged as an alternative class of highly active monomers for polyester polymerization. OCAs are prepared from amino acids and thus have a richer range of side chain functionalities than lactone or lactide. Like lactones, OCAs can undergo ROP to obtain polyesters. Unfortunately, current ROP methods, especially those involving organocatalysts, result in uncontrolled polymerization including epimerization for OCAs bearing electron-withdrawing groups, unpredictable molecular weights (MWs), or slow polymerization kinetics. Based on our recent success of Ni/Ir photoredox catalysis allowing for rapid synthesis of high-MWs polyesters, we further explore new polymerization chemistry to use earth-abundant metal complexes to replace expensive rare-earth metal photocatalysts, and practice the polymerization in moderate and energy-efficient reaction conditions. This thesis introduces novel photoredox and electrochemical earth-abundant metal catalysts that overcome above difficulties in the ROP chemistry of OCAs, and allow for the preparation of stereoregular polyesters bearing abundant side-chain functionalities in a highly controlled manner. Specifically, various highly active metal complexes have been developed for stereoselective ROP of OCAs, either using light or electricity, to synthesize syndiotactic or stereoblock copolymers with different thermal properties. Additionally, simple purification protocols of OCAs have also been initially studied, which potentially paves the way to bulk production of functional monomers. In this thesis, I first describe newly-developed photoredox Co/Zn catalysts to achieve a controlled ROP of enantiopure OCAs under mild reaction conditions (Chapter 2). Such discovery is extended to the combination use of Co catalysts with various Zn/Hf complexes that enable stereoselective controlled ROP of racemic OCAs for the preparation of stereoregular polyesters (Chapter 3). The mechanistic studies of the aforementioned developments lead to the application of such a catalytic system in controlled electrochemical ROP of OCAs (Chapter 4). Such chemistry can also be translated to stereoselectively electrochemical ROP of racemic OCAs to either syndiotactic or stereoblock polyesters, allowing precise control of polyester's tacticity and sequence (Chapter 5). An overview future work has been summarized (Chapter 6). / Doctor of Philosophy / Polyesters are widely used in everyday applications ranging from clothing and packaging to agriculture and biomedicine. Different from conventional unrecyclable plastics, polyesters are usually biocompatible and biodegradable, and can be synthesized from renewable resources. A few commercially available polyesters have been approved by FDA and widely used for medical applications. However, their utility for applications that demand various mechanical and chemical properties is greatly limited by the lack of side-chain functional groups in polyesters and in their monomers—lactones. Increasing efforts have been devoted to the introduction of pendant groups along the polymer chain in order to modify and modulate the desired properties of polyesters and thereby to expand their applications. Over the last decade, O-carboxyanhydrides (OCAs) have emerged as an alternative class of highly active monomers for polyester polymerization. OCAs can be prepared from renewable source amino acids and thus have a richer range of side chain functional groups. Like lactones, OCAs can undergo ring-opening polymerization (ROP). Unfortunately, current ROP methods usually result in uncontrolled polymerization of OCAs including loss of stereoregularity, unpredictable molecular weights, or slow polymerization rate. To address the above-described polymer chemistry and materials challenges, I have been motivated to develop a new polymer chemistry knowledge base when starting my Ph.D. program. I was first involved in the development of a controlled photoredox polymerization of OCAs produces polyesters with various side chain functional groups. By using photoredox Ni/Zn/Ir catalysts, stereoregular high molecular weight polyesters can be synthesized from racemic OCAs in a rapid, controlled manner. However, this catalytic system has to be used at -20 °C despite so successful in preparing stereoblock polyesters. Encouraged by our recent success in this area, I started to work on the discovery of other transition metal complexes such as the Co complexes used in N-carboxyanhydride polymerization. Ultimately, innovative photoredox Co/Zn catalysts has been successfully developed, and applied to our protocol to achieve the controlled ROP of enantiopure OCAs under mild reaction condition (Chapter 2). The Co catalyst can replace both Ni and Ir in aforementioned photoredox system. Meanwhile, the combination of Co catalysts and various Zn/Hf complexes has also been developed to undergo photoredox ROP of racemic OCAs to efficiently produce polyesters with different microstructures (Chapter 3). Although photoredox ROP is an efficient method for synthesizing degradable polyesters, great decrease in photonic flux with the depth of the reaction medium makes it less energy efficient compared to electricity. Therefore, we then extended our protocol to electrochemical reaction, which is one of the most energy-efficient chemical reactions. The newly identified Co/Zn catalytic system can be activated by electric current to mediate rapid electrochemical ROP (eROP) of enantiopure OCAs, allowing for the synthesis of isotactic polyesters in a highly controlled manner (Chapter 4). Additionally, stereoselective eROP of racemic OCAs has been firstly achieved by using various combinations of Co and Zn/Hf complexes (Chapter 5). In summary, my research produces unique and transformative insights into the innovative photoredox and electrochemical ROP mediated by metal catalysts. Given the importance and versatility of biodegradable and biocompatible polyester materials, the chemistry invented by our team can be expected to serve as a new platform for various applications in material and biomedical engineering.

<p dir="ltr">Aromatic phosphonates and phosphine oxides are highly desirable synthetic targets used in pharmaceuticals, natural products, agrichemicals, catalysis, and materials science. While a variety of aromatic precursors have been used to access these motifs, aryl halides remain one of the most desirable coupling partners owing to their low cost, commercial availability, and regioselective reactivity. Traditional phosphonation often requires the use of harsh reductants in the presence of liquid ammonia, which are caustic and pose incredible environmental concerns. Milder, transition metal-catalyzed approaches have been developed, but can be limited by air sensitivity, cost, low reaction selectivity, and low functional group compatibility. Photoredox catalysis has been significantly advanced in the past decade in the pursuit of greener, more sustainable avenues to facilitate desirable reaction transformations under mild conditions. These methods most commonly use a dual catalytic strategy in which a metal is paired with an organocatalyst. While these approaches enable facile phosphonation of a variety of aromatic precursors, the metals and organocatalysts used are often expensive and toxic. Indeed, there remains unexplored chemical space for transition metal-free photoredox-catalyzed aryl C-P bond formations. Herein, we present a series of transition metal-free, photoredox-catalyzed approaches to the phosphonation of aryl halides. The approaches and mechanistic works will be discussed in the following order: </p><p dir="ltr">First, the discovery that 10<i>H</i>-phenothiazine (PTZ) enables the transition metal-free phosphonation of aryl halides using trialkyl phosphites will be presented. PTZ serves as a photocatalyst capable of reducing the aryl halide to access aryl radicals, which readily couple with phosphite esters. This transformation exhibits broad functional group tolerance in good to excellent yields. Then, photoredox catalysis by PTZ enables the formation of unsymmetrical aromatic phosphine oxides using triphenylphosphine (PPh₃) and aryl halides. This is the first work in which PPh₃ has been used as the starting material, and the reaction proceeds via the alkaline hydrolysis of quaternary phosphonium salts. The final work exhibits novel photocatalytic activity of <i>N</i>-heterocyclic carbenes (NHC) to activate aryl halides, form aryl radicals, and enable phosphonation. This method displays broad functional group tolerance under mild conditions and highlights its untapped synthetic utility as a photocatalyst.</p>

Ce projet scientifique concerne le développement de nouvelles méthodes efficaces de fonctionnalisation d’imines par des procédés organocatalysés et photocatalysésDans un premier temps la réaction photocatalysée d’alkylation d’énamines en conditions douces à été étudiée. L’utilisation de photocatalyseurs sous forme de complexes organométalliques d’Iridium a permis de réaliser la double fonctionnalisation d’ènecarbamates, permettant ainsi d’obtenir des substituts d’imines hautement substitués. Ce procédé permet de s’affranchir de l’utilisation de métaux lourds et ne nécessite qu’une activation par la lumière visible pour fonctionner. Cette transformation radicalaire éco-compatible à par la suite été soumise à une étude mécanistique approfondie. Dans une deuxième partie, la réaction d’aza-Friedel-Crafts organocatalysée par des acides de Brønsted chiraux à été étudiée. Dans cette réaction, la bi-fonctionnalité des acides chiraux dérivés du BINOL a été exploitée. Elle permet l’addition énantiosélective d’une grande variété d’indoles substitués sur des acyl-pyrrolidinones générées in situ. Les composés synthétisés présentent des structures bioactives intéressantes notamment sur le système nerveux central.Enfin, la première réaction de Povarov asymétrique impliquant des amino-hétérocycles comme précurseurs de 2-azadiènes à été décrite. Cette étude s’appuie sur des travaux antérieurs du laboratoire et permet la synthèse des analogues hétérocycliques de tétrahydroquinoléines précédemment décrites. Le procédé met en jeu une séquence multicomposants réduction/Povarov catalysée par des acides phosphoriques chiraux et permet l’accès rapide à une large bibliothèque d’analogues. / The aim of this study is the development of new methodologies for imines functionalization by organocatalysed and photocatalysed processes.First, a photocatalysed alkylation reaction of enecarbamates have been described. The use of organometallic Iridium complexes allowed the double functionalization of enecarbamates leading to highly substituted imines surrogates. This process is a green alternative to the use of heavy metals and only needs visible light as an renewable energy source to proceed. This environment-friendly radical transformation has been submitted to mechanistic study.In a second part, an aza-Friedel-Crafts reaction organocatalysed by chiral Brønsted acid has been studied. The bi-fonctionnality of chiral phosphoric acids has been advantageously used to perform the Friedel-Crafts addition of various substituted indole to in situ generated acyl-iminium ions. The compounds obtained by this methodology are showing interesting biological activities on central nervous system. Finally, the first enantioselective Povarov reaction involving amino-heterocycles as 2-azadienes precursors has been reported. This reaction is based on previous lab reports and the synthesis of tetrahydroquinoline analogues has been described. The multicomponent reduction/Povarov reaction sequence catalyzed by chiral phosphoric acids derived gives a rapid access to a wide library of bioactives analogues.

Dans le cadre de la synthèse totale de la leucophyllidine, un alcaloïde bis-indolique, des réactions de carbo- et sulfonyl-cyanation radicalaires sans étain ont été développées. Les cyanures de sulfonyle RSO2CN, préparés à partir des thiocyanates correspondant par une nouvelle méthode d’oxydation, sont utilisés comme pièges radicalaires. Ces réactifs fragmentent en présence d’initiateur thermique (carbo-cyanation) ou par le biais de la catalyse photoredox (sulfonyl-cyanation). Dans ce dernier cas, une étude mécanistique approfondie sur le cycle photo-catalytique a été accomplie. Ces méthodologies introduisent un nitrile sur une chaîne carbonée insaturée par voie radicalaire, fournissant des intermédiaires avancés pour la synthèse totale d’alcaloïdes. Pour la synthèse asymétrique de l’eucophylline, le fragment sud de la leucophyllidine, la sulfonyl-cyanation de cyclobutènes énantioenrichis a montré d’excellentes diastéréosélectivités. Différentes stratégies d’ouverture de cycle ont ensuite été examinées. / During our efforts directed toward the total synthesis of leucophyllidine, a bis-indole alkaloid, the tin-free radical carbo-cyanation and sulfonyl-cyanation of olefins were developed. The sulfonyl cyanides, acting as radical traps, were synthesized through a new oxidation of the corresponding thiocyanate. These reagents were found to fragment under thermal initiation (carbo-cyanation) or using the photoredox catalysis (sulfonyl-cyanation). A thorough mechanistic study was accomplished for the sulfonyl-cyanation. These methodologies install a nitrile onto an olefin backbone, furnishing advanced intermediates for the total synthesis of alkaloids. For the asymmetric synthesis of eucophylline, the south fragment of leucophyllidine, the sulfonyl-cyanation of optically pure cyclobutenes showed excellent diastereoselectivities. Different ring-opening reactions of the corresponding cyclobutane were then examined.

No description available.

The discovery and mechanistic investigation of a new class of photochemical reactions of benzophenones and related compounds is documented in this Thesis. Their photobehaviour in aqueous solvent media varied dramatically from their well-known behaviour in organic solvents and suggests unique and unprecedented mechanistic pathways. The aqueous photoredox chemistry of various substituted benzophenones was initially explored. Particular attention was paid to 3-(hydroxymethyl)benzophenone (47), which upon photolysis in acidic aqueous media undergoes an intramolecular photoredox reaction to produce 3-formylbenzhydrol (61). Extensive investigation into the mechanistic behaviour of 3-(hydroxymethyl)benzophenone (47) produced evidence of a unique solvent-mediated, acid catalysed photoreaction. A mechanism has been proposed for the intramolecular photoredox reaction that proceeds via the protonated triplet state. This protonated triplet state subsequently promotes the deprotonation of the benzylic carbon before rearranging to form the redox product. The modification of the benzylic carbon with an alkyl group or with a phenyl group resulted in only slight changes in the photobehaviour. In both cases intramolecular photoredox reactions were observed although significantly more oligomeric side products were observed in some cases. To more fully elucidate the photobehaviour and to test the generality of the photoredox reaction, a variety of structurally related hydroxyalkyl aromatic carbonyls were synthesized and studied. Alternative chromophores were explored using xanthone and fluorenone derivatives. Both types of derivative compounds underwent an intramolecular photoredox reaction, supporting the assertion that the intramolecular photoredox reaction could be considered a general feature of aromatic carbonyls under aqueous conditions. However, significant differences in photoreactivity were also observed. It was found that 2-(hydroxymethyl)xanthone (53) exhibited sufficient photoactivity that the intramolecular photoredox reaction was observable even under neutral conditions whereas 2-(hydroxymethyl)fluorenone (54) was nearly photoinert. The last topic focuses on the extension of the electronic transmission from the carbonyl functional group to the benzylic alcohol by insertion of an additional phenyl group. The addition of the phenyl group also provided a bichromophoric molecule, rather than the monochromophoric substrates studied to this point. The substituent’s position played an important role in the photobehaviour, in that both of the meta- and ortho- substituted compounds underwent intramolecular photoredox reaction, while the para- substituted compound primarily exhibited photobehaviour indicative of hydrogen abstraction.