Ung Chan Yoon

Studies Leading to the Development of a Single-Electron Transfer (SET) Photochemical Strategy for Syntheses of Macrocyclic Polyethers, Polythioethers, and Polyamides

Organic photochemists began to recognize in the 1970s that a new mechanistic pathway involving excited-state single-electron transfer (SET) could be used to drive unique photochemical reactions. Arnolds seminal studies demonstrated that SET photochemical reactions proceed by way of ion radical intermediates, the properties of which govern the nature of the ensuing reaction pathways. Thus, in contrast to classical photochemical reactions, SET-promoted excited-state processes are controlled by the nature and rates of secondary reactions of intermediate ion radicals. In this Account, we discuss our work in harnessing SET pathways for photochemical synthesis, focusing on the successful production of macrocyclic polyethers, polythioethers, and polyamides. One major thrust of our studies in SET photochemistry has been to develop new, efficient reactions that can be used for the preparation of important natural and non-natural substances. Our efforts with α-silyl donor-tethered phthalimides and naphthalimides have led to the discovery of efficient photochemical processes in which excited-state SET is followed by regioselective formation of carbon-centered radicals. The radical formation takes place through nucleophile-assisted desilylation of intermediate α-silyl-substituted ether-, thioether-, amine-, and amide-centered cation radicals. Early laser flash photolysis studies demonstrated that the rates of methanol- and water-promoted bimolecular desilylations of cation radicals (derived from α-silyl electron donors) exceeded the rates of other cation radical α-fragmentation processes, such as α-deprotonation. In addition, mechanistic analyses of a variety of SET-promoted photocyclization reactions of α-silyl polydonor-linked phthalimides and naphthalimides showed that the chemical and quantum efficiencies of the processes are highly dependent on the lengths and types of the chains connecting the imide acceptor and α-silyl electron donor centers. We also observed that reaction efficiencies are controlled by the rates of desilylation at the α-silyl donor cation radical moieties in intermediate zwitterionic biradicals that are formed by either direct excited-state intramolecular SET or by SET between the donor sites in the intervening chains. It is important to note that knowledge about how these factors govern product yields, regiochemical selectivities, and quantum efficiencies was crucial for the design of synthetically useful photochemical reactions of linked polydonor-acceptor substrates. The fruits of these insights are exemplified by synthetic applications in the concise preparation of cyclic peptide mimics, crown ethers and their lariat- and bis-analogs, and substances that serve as fluorescence sensors for important heavy metal cations.

Nature and kinetic analysis of carbon-carbon bond fragmentation reactions of cation radicals derived from SET-oxidation of lignin model compounds.

Features of the oxidative cleavage reactions of diastereomers of dimeric lignin model compounds, which are models of the major types of structural units found in the lignin backbone, were examined. Cation radicals of these substances were generated by using SET-sensitized photochemical and Ce(IV) and lignin peroxidase promoted oxidative processes, and the nature and kinetics of their C-C bond cleavage reactions were determined. The results show that significant differences exist between the rates of cation radical C1-C2 bond cleavage reactions of 1,2-diaryl-(β-1) and 1-aryl-2-aryloxy-(β-O-4) propan-1,3-diol structural units found in lignins. Specifically, under all conditions C1-C2 bond cleavage reactions of cation radicals of the β-1 models take place more rapidly than those of the β-O-4 counterparts. The results of DFT calculations on cation radicals of the model compounds show that the C1-C2 bond dissociation energies of the β-1 lignin model compounds are significantly lower than those of the β-O-4 models, providing clear evidence for the source of the rate differences.

Production of superoxide from Photosystem II in a rice ( Oryza sativa L.) mutant lacking PsbS

BackgroundPsbS is a 22-kDa Photosystem (PS) II protein involved in non-photochemical quenching (NPQ) of chlorophyll fluorescence. Rice (Oryza sativa L.) has two PsbS genes, PsbS1 and PsbS2. However, only inactivation of PsbS1, through a knockout (PsbS1-KO) or in RNAi transgenic plants, results in plants deficient in qE, the energy-dependent component of NPQ.ResultsIn studies presented here, under fluctuating high light, growth of young seedlings lacking PsbS is retarded, and PSII in detached leaves of the mutants is more sensitive to photoinhibitory illumination compared with the wild type. Using both histochemical and fluorescent probes, we determined the levels of reactive oxygen species, including singlet oxygen, superoxide, and hydrogen peroxide, in leaves and thylakoids. The PsbS-deficient plants generated more superoxide and hydrogen peroxide in their chloroplasts. PSII complexes isolated from them produced more superoxide compared with the wild type, and PSII-driven superoxide production was higher in the mutants. However, we could not observe such differences either in isolated PSI complexes or through PSI-driven electron transport. Time-course experiments using isolated thylakoids showed that superoxide production was the initial event, and that production of hydrogen peroxide proceeded from that.ConclusionThese results indicate that at least some of the photoprotection provided by PsbS and qE is mediated by preventing production of superoxide released from PSII under conditions of excess excitation energy.

Single Electron Transfer-Promoted Photocyclization Reactions of Linked Acceptor−Polydonor Systems: Effects of Chain Length and Type on the Efficiencies of Macrocyclic Ring-Forming Photoreactions of Tethered α-Silyl Ether Phthalimide Substrates

Results of an investigation, aimed at gaining information about the factors governing the efficiencies of single electron transfer (SET)-promoted photocyclization reactions of linked acceptor-polydonor systems, are described. One set of substrates used in this effort includes alpha-trimethylsilyl ether terminated, polymethylene- and polyethylenoxy-tethered phthalimides and 2,3-naphthalimides. Photocyclization reactions of the polyethylenoxy-linked phthalimides and naphthalimides were observed to take place in higher chemical yields and with larger quantum efficiencies than those of analogs containing polymethylene tethers of near equal length. These findings show that the rates of formation of 1,omega-zwitterionic biradicals that serve as key intermediates in the photocyclization processes are enhanced in substances that contain oxygen donor sites in the chain. The findings suggest that these donor sites facilitate both initial SET to acceptor excited states and ensuing intrachain SET, resulting in migration of the cation radical center to the terminal alpha-trimethylsilyl ether position. In addition, an inverse relationship was observed between the quantum yields of photocyclization reactions of the tethered phthalimides and naphthalimides and the length of the polyethylenoxy chain. Finally, the roles played by chain type and length in governing photoreaction efficiencies were investigated by using intramolecular competition in photoreactions of polyethylenoxy and polymethylene bis-tethered phthalimides. Mechanistic interpretations and synthetic consequences of the observations made in this study are discussed.

Single electron transfer-induced photocyclization reactions of N-[(N-trimethylsilylmethyl)aminoalkyl]phthalimides

Abstract Studies have been conducted to explore single electron transfer (SET) induced photocyclization reactions of N -[( N -acetyl- N -trimethylsilylmethyl)amidoalkyl]phthalimides (alkyl≡ethyl, n -propyl, n -pentyl and n -hexyl) and N -[( N -mesyl- N -trimethylsilylmethyl)amidoethyl]phthalimide. Photocyclizations occur on irradation of these substances in methanol in modest to high yields to produce cyclized products in which the phthalimide carbonyl carbon has become bonded to the carbon of the side chain in place of the trimethylsilyl group. A mechanism for these photocyclization reactions involving intramolecular SET from nitrogen in the α-silylamido group to the singlet excited state of the phthalimide followed by desilylation of the intermediate α-silylamido cation radical and cyclization by radical coupling is proposed. Furthermore, photoreactivity of N -[( N -methyl- N -trimethylsilylmethyl)aminoethyl]phthalimide differs from the other members of this series. Here a route involving triplet hydrogen atom abstraction predominates over that involving sequential singlet SET-desilylation. A relationship between the quantum efficiencies for reactions of the phthalimides with various α-silyl- n -electron donors and the oxidation potentials of the electron donors has been noted. The results suggest that the rate of desilylation of the cation radical intermediate is an important factor in determining the quantum efficiency of the SET-induced photoreaction and that the desilylation rates are directly proportional to the oxidation potentials of the donors. The efficient and regioselective cyclization reactions observed for photolyses in methanol represent synthetically useful processes for construction of medium and large ring heterocyclic compounds.

Photoaddition Reactions of 1,2-Diketones with Silyl Ketene Acetals. Formation of β-Hydroxy-γ-ketoesters

Photochemical reactions taking place between 1,2-diketones and silyl ketene acetals and their excited state reaction mechanisms have been explored. Irradiation of benzene, acetone, or acetonitrile solutions containing 1,2-diketones and silyl ketene acetals is observed to promote formation of 1,4-dioxenes, resulting from [4 + 2]-cycloaddition, oxetanes, arising by Paterno-Buchi processes, and beta-hydroxy-gamma-ketoesters, generated by SET-promoted Claisen-type condensation. These competitive pathways leading from the excited states of the 1,2-diketones to these products are influenced by solvent polarity and the nature of the silyl ketene acetal and 1,2-diketone. The Claisen-type condensation process, following an SET desilylation pathway and predominating when the photoreactions are carried out in the polar solvent acetonitrile, represents an efficient method to prepare a variety of diversely substituted beta-hydoxy-gamma-ketoesters.

Electron Transfer - Induced Photochemical Reactions in Imide- RXCH2 TMS Systems. Photoaddition of a-Trimethylsilyl Substituted Heteroatom Containing Compounds to Phthalimides

Reaction de phtalimides avec des R trimethyl silanes (R=ethoxymethyl, propylthiomethyl, diethylaminomethyl); obtention de phtalimidines

Regioselectivity of enzymatic and photochemical single electron transfer promoted carbon-carbon bond fragmentation reactions of tetrameric lignin model compounds.

New types of tetrameric lignin model compounds, which contain the common β-O-4 and β-1 structural subunits found in natural lignins, have been prepared and carbon-carbon bond fragmentation reactions of their cation radicals, formed by photochemical (9,10-dicyanoanthracene) and enzymatic (lignin peroxidase) SET-promoted methods, have been explored. The results show that cation radical intermediates generated from the tetrameric model compounds undergo highly regioselective C-C bond cleavage in their β-1 subunits. The outcomes of these processes suggest that, independent of positive charge and odd-electron distributions, cation radicals of lignins formed by SET to excited states of sensitizers or heme-iron centers in enzymes degrade selectively through bond cleavage reactions in β-1 vs β-O-4 moieties. In addition, the findings made in the enzymatic studies demonstrate that the sterically large tetrameric lignin model compounds undergo lignin peroxidase-catalyzed cleavage via a mechanism involving preliminary formation of an enzyme-substrate complex.

Effects of alkoxy groups on arene rings of lignin β-O-4 model compounds on the efficiencies of single electron transfer-promoted photochemical and enzymatic C-C Bond Cleavage Reactions.

To gain information about how alkoxy substitution in arene rings of β-O-4 structural units within lignin governs the efficiencies/rates of radical cation C1-C2 bond cleavage reactions, single electron transfer (SET) photochemical and lignin peroxidase-catalyzed oxidation reactions of dimeric/tetrameric model compounds have been explored. The results show that the radical cations derived from less alkoxy-substituted dimeric β-O-4 models undergo more rapid C1-C2 bond cleavage than those of more alkoxy-substituted analogues. These findings gained support from the results of DFT calculations, which demonstrate that C1-C2 bond dissociation energies of β-O-4 radical cations decrease as the degree of alkoxy substitution decreases. In SET reactions of tetrameric compounds consisting of two β-O-4 units, containing different degrees of alkoxy substitution, regioselective radical cation C-C bond cleavage was observed to occur in one case at the C1-C2 bond in the less alkoxy-substituted β-O-4 moiety. However, regioselective C1-C2 cleavage in the more alkoxy-substituted β-O-4 moiety was observed in another case, suggesting that other factors might participate in controlling this process. These observations show that lignins containing greater proportions of less rather than more alkoxylated rings as part of β-O-4 units would be more efficiently cleaved by SET mechanisms.

Surface-induced alignment of pentacene by photo-alignment technology for organic thin film transistors

A series of highly soluble maleimide-based polymers with photoreactive pendant group were synthesized and used as a gate dielectric insulator for organic thin film transistors. Photoalignment properties were characterized by UV-visible spectroscopy and the alignment of liquid crystals. Photopolymerization of polymer-coated organic thin film transistors with linearly polarized UV light induces anisotropy in field-effect mobility. The gate dielectric insulator based on the photoalignable maleimide shows higher field-effect mobility and on/off current ratio than those from a SiO2 gate dielectric insulator with the values of 0.3 cm2 V−1 s−1 and 104, respectively. Our results demonstrate that the photo-induced anisotropy of alignment films to control the molecular order of semiconducting pentacene is a promising technology for improving the performance of organic thin film transistors.