다중혈관 관상동맥 환자에서 y-문합을 이용하여 양쪽 내흉동맥만을 사용한 우회술의 조기 성적

Switches, and Actuators Masahiro Irie,*,† Tuyoshi Fukaminato,‡ Kenji Matsuda, and Seiya Kobatake †Research Center for Smart Molecules, Rikkyo University, Nishi-Ikebukuro 3-34-1, Toshima-ku, Tokyo 171-8501, Japan ‡Research Institute for Electronic Science, Hokkaido University, N20, W10, Kita-ku, Sapporo 001-0020, Japan Department of Synthetic Chemistry and Biological Chemistry, Graduate School of Engineering, Kyoto University, Katsura, Nishikyo-ku, Kyoto 615-8510, Japan Department of Applied Chemistry, Graduate School of Engineering, Osaka City University, Sugimoto 3-3-138, Sumiyoshi-ku, Osaka 558-8585, Japan

Photochromism of Diarylethene Molecules and Crystals: Memories, Switches, and Actuators

ed from in the transition state. This answers the question of both the retention and the inversion of stereochemistry for the simple exchange reaction giving back I (which it should be noted is highly disfavored because k2 ≫ k−1). Retention of configuration would occur by first noting that the potassium ion would also be coordinated to the same face as the abstracted hydrogen atom because it was originally coordinated to the oxygen of the base. A molecule of deuterated alcohol can then approach this same face through coordination to the potassium. Rotation of these ligands around potassium would result in the deuterated alcohol now hydrogen bonded to the allylic anion (IV-top), which following collapse would return the chiral alkene I-d with the same configuration. On the other hand, inversion of stereochemistry would occur via the deuterated solvent approaching from the face of the allylic anion opposite to that hydrogen bonded, and exchange with the alcohol giving (IV-bottom). This could collapse and give chiral alkene I-d with inversion of configuration. The E/Z ratio of 60 for product III-h is also important because this value is extremely high as compared to the equilibrium value of 4.2 for the diastereoisomers, and compares to other systems as well. For example, the isomerization of allylbenzene into 1-propenylbenzene has an E/Z ratio of 44 when using potassium t-butoxide in DMSO. The reason for this higher-than-equilibrium ratio is explained in Scheme 3. Two “conformations” of the chiral alkene I are suitable for deprotonation and will lead to either the E or the Z allylic anions as shown. The rate of “conformational rotation” must be many orders of magnitude greater than the rates for Scheme 2. Proposed Base-Mediated Reaction Mechanism Scheme 3. Interactions Leading to Observed E/Z Ratios Chemical Reviews Review DOI: 10.1021/acs.chemrev.5b00052 Chem. Rev. XXXX, XXX, XXX−XXX E deprotonation (kE and kZ), and thus the E/Z ratio in the product must be related to the kE/kZ ratio. The transition state leading to the Z-allylic anion must thus be higher in energy than the one leading to the E-allylic anion, presumably due to the disfavored 1,3-allylic interactions, which would make charge stabilization through conjugation more difficult. Cram has reported this in more detail, including an analysis of collapse ratios (i.e., ratio of protonation of either carbon on the allylic anion), the stereochemical stability of allylic and vinyl anions, and the kinetic and thermodynamic stabilities of olefinic products formed by protonation of allylic anions. 2.2. Transition Metal-Mediated Mechanisms The mechanisms for the transition metal-mediated isomerizations have in some cases been very carefully determined, while in many they are assumed from one of two generally accepted pathways (Schemes 4 and 5). The first involves a discrete transition metal−hydride active catalyst and the formation of a transition metal−alkyl intermediate, while the second involves the formation and collapse of a η-allyl hydride complex. Each of the mechanisms described below bases its premise on the fact that each step is reversible, and thus the reactions are under thermodynamic control at equilibrium. 2.2.1. Alkyl Mechanism. For this mechanism to occur, the transition metal catalyst must have both an empty 2e− coordination site (e.g., via dissociation of a ligand) and a metal hydride bond that is typically generated in situ under the reaction conditions (see Scheme 4). The catalyst first coordinates to the π-electrons of the alkene followed by an insertion reaction to give either a primary or a secondary metal−alkyl intermediate. The primary metal−alkyl is generally formed faster for many catalysts, but is a mechanistic dead-end returning the starting material through β-hydride elimination and is thus a nonproductive pathway. The secondary metal− alkyl intermediate can however produce either the Eor the Z1-propenylbenzene on β-hydride elimination, which is clearly thermodynamically favored because of the conjugation to the benzene ring. 2.2.2. Allyl Mechanism. The allyl mechanism, however, requires a transition metal capable of having two vacant coordination sites, and, more specifically, no metal−hydride should be present or the alkyl mechanism will take place (see Scheme 5). The first step involves coordination of the πelectrons of the allylbenzene to one of the transition metal’s vacant sites. This is followed by an oxidative addition reaction giving an η-allyl metal−hydride complex, which can collapse to either the starting material or the rearranged and thus more stable alkene. The η-complex may also rearrange to the ηcomplex as part of the reaction pathway. The difference between these two mechanisms can be determined through deuterium labeling with 32 and crossover experiments (Scheme 6). The allyl mechanism is entirely intramolecular and involves an effective 1,3-hydride shift as the only mechanistic pathway. Thus, in a crossover experiment, such as that in Scheme 6, the deuterium should (a) only be found at the 1and 3-positions of the allylic system, that is, 34, and (b) not be incorporated into the second nondeuterated substrate. In the case of the alkyl mechanism, products similar to those of the allyl mechanism may be detected in addition to (a) the nondeuterated substrate showing some deuterium incorporation and (b) the loss of deuterium and incorporation of hydrogen on the deuterated substrate. Furthermore, deuterium incorporation at the 2-position of the allylic system, 35, is also expected because the initial metal−hydride insertion reaction may have poor regioselectivity as already explained in Scheme 2. Of course it should be noted that these two general mechanisms are just that, and the specific reaction pathway for different transition metal catalysts will depend heavily on the transition metal, ligand, solvent, and substrate combinations. More detailed mechanistic data can be obtained from kinetic studies supplemented by state-of-the-art measurements, for example, nanosecond time-resolved IR, NMR, and DFT calculations. These studies have invariably revealed Scheme 4. Alkyl Mechanism M = transition metal; [L]n = bound ligand(s); [L]0 = dissociating ligand or vacant 2e− site. Scheme 5. Allyl Mechanism M = transition metal; [L]n = bound ligand(s); [L]0 = dissociating ligand or vacant 2e− site. Chemical Reviews Review DOI: 10.1021/acs.chemrev.5b00052 Chem. Rev. XXXX, XXX, XXX−XXX F mechanisms more complicated than those presented above, but at the same time generally holding true to them. One major mechanistic departure has been that proposed by Harvey and Lloyd-Jones in which they suggest a binuclear palladium complex being involved in the E/Z isomerization of alkenes. However, it should be noted that this is only applicable in some cases. More important is that the specific mechanisms themselves answer questions related to E/Z selectivity in these transition metal-mediated isomerizations. Simplistically, the reactions can be considered to be under thermodynamic control, and therefore the E/Z ratios will favor the E-isomer. The π-allyl mechanism has been linked, in a general sense, with higher E/Z ratios, but can by no means be used as proof for a particular mechanism. This is because the E/Z selectivity in the reaction is strongly governed not only by the thermodynamic stability of the E isomer (and intermediates leading to the E-isomer), but can be shifted through ligand and or kinetic control to high ratios of either the E or the Z isomers. The sections below detailing the specific examples in the literature will highlight these selectivities. 3. ISOMERIZATION METHODS − GENERAL Perusal of the literature quickly confirms that 2-propenylaryl isomerization reactions have been promoted by mainly two classes of methods, viz., the application of bases (section 4) or transition metal complexes (section 5). In this Review, these sections will thus be discussed separately, in addition to a final section describing miscellaneous allylaryl isomerizations (section 6). In each section, substrates of particular interest will be highlighted, with particular care being taken to convey important experimental data such as yields, the cis/trans ratios obtained, and any other relevant information. 4. BASE-MEDIATED ISOMERIZATIONS In general, base-initiated reactions require at least a stoichiometric amount of base to accomplish the isomerization of an allylbenzene. This method has seen much application in the past literature, and some general information has been collated in book chapters. 4.1. Hydroxide/Alkoxide Ion-Mediated Isomerizations This particular method involves the use of fairly harsh reaction conditions in that it generally comprises heating the substrate in a protic solution (ethanol, methanol, or n-butanol) of sodium or potassium hydroxide (giving rise to a mixture of the hydroxide and corresponding alkoxide under equilibrium conditions). Other examples include the use of hydroxide in DMSO. Of interest is that the KOH/ethylene glycolmediated isomerization of eugenol 5 has actually been incorporated into the curriculum of a teaching laboratory to demonstrate how the kinetics of a reaction can be studied using NMR spectroscopic, GC, and HPLC laboratory techniques. It should also be mentioned here that the importance of the potassium t-butoxide system means that a separate subsection will be dedicated to this method (see section 4.2). In the first section, examples of where hydroxide-mediated isomerization has been applied will be highlighted. This will be followed by methods in which the isomerization approach has been modified, albeit with additives (phase transfer), microwave heating, or different solvent systems. 4.1.1. Hydroxide/Alkoxide Ions in Alcohol (Methanol, Ethanol, n-Butanol) or without Solvent. It should be noted that the use of sodium ethoxide has been rigorously studied, showing that the isomerization of para-substi

Isomerization of allylbenzenes.

The design and synthesis of a series of photochromic diarylethene-containing Arduengo-type N-heterocyclic carbenes (NHCs) of gold(I), silver(I) and palladium(II) and their imidazolium salt precursors are reported. Reversible photochromic behavior was observed. The open form and the closed form also show different luminescence properties. The electronic and conformational/steric changes associated with the photocyclization and photocycloreversion reactions may open up new opportunities for the discovery of new classes of photochromic ligands and metal-containing materials and catalysts with photoswitchable functions and activities and regio-/enantioselectivities.

Photochromic Diarylethene-Containing Ionic Liquids and N-Heterocyclic Carbenes

In the cascade of mammalian vision, the cis-to-trans photoisomerization reaction of the retinal chromophore bound to the opsin apoprotein acts as the first trigger for the conversion of light signals into electrical pulses, which are finally transmitted to the brain. One of the specific chemical characteristics of retinal chromophore is its high quantum yield of cis-to-trans photoisomerization, Fcis–trans = 65 %, which affords the high sensitivity of the rod rhodopsin, an opsin–retinal complex required for night vision. Interestingly, the Fcis–trans value of retinal decreased to less than 30% in solution without the protein. This observation suggests that the environmental conditions of the binding pocket in rhodopsin may be responsible for the high photochemical reactivity of retinal. The hydrophobic pocket in rhodopsin is thought to favor appropriate noncovalent bonding to regulate the geometry of the guest molecule in preparation for the photoisomerization reaction. With the aim of developing highly efficient and sensitive photochromic molecules on the basis of the opsin–retinal system, we designed an organic photochromic molecule with a terarylene structure and demonstrated its photon-quantitative reaction. Photochromic terarylenes are composed of three aromatic rings connected to form a hexatriene backbone, which is converted into a cyclohexadiene structure upon UV irradiation, as similarly observed for the photochromism of diarylethenes. Recent studies on terarylenes have highlighted their high photocyclization quantum yields, which exceed 60% 5] and are apparently higher than those of conventional diarylethenes. Since the photoelectrocyclic reactions typically occur in less than 200 fs, the photocyclization quantum yield is generally determined by the electronic structure in the excited state, which is directly interpreted as the molecular conformation in the ground state. Diarylethenes are known to possess two conformations in solution, with the two rings in mirror symmetry (parallel conformation) or C2 symmetry (antiparallel conformation). As the photocyclization reaction proceeds only from the C2-symmetrical conformation, the quantum yield is about 50% at most. In contrast, some diarylethenes undergo a quantitative photocyclization reaction in the crystalline state, when their conformation is fixed in the antiparallel conformation and the distance between reactive carbon atoms is sufficiently short: typically less than 0.4 nm. These observations indicate that the ground-state conformation plays a crucial role in the photoinduced pericyclization reaction. Therefore, various attempts have been made to regulate the ground-state geometry of diarylethenes so that they have C2 symmetry. [7] We herein propose a concept for the design of highly reactive photochromic hexatriene molecules that is inspired by the design of foldamers; thus, multiple intramolecular interactions were used to stabilize the photoreactive conformation of a terarylene. The 2,3-dithiazolylbenzothiophene 1a was designed as a representative photochromic molecule whose conformation is expected to be stabilized in the photoreactive conformation through intramolecular interactions, as depicted by dotted lines in Scheme 1. The rotation of one side-chain thiazolyl

Photon-Quantitative Reaction of a Dithiazolylarylene in Solution

Procedures for the synthesis of 4,5-bis[2,5-dimethyl(3-thienyl)]-1,3-azoles based on 1,2-bis[2,5-dimethyl(3-thienyl)]-2-hydroxyethan-1-one, 2-chloro-1,2-bis[2,5-dimethyl(3-thienyl)]ethan-1-one, and 1,2-bis[2,5-dimethyl(3-thienyl)]ethane-1,2-dione were developed. Dithienylethenic compounds in which the thienyl rings are linked through the azole rings exhibit photochromic properties.

Photochromic dihetarylethenes. 7. Synthesis of bis(thienylazoles), photochromic analogs of diarylethenes

Herein, we report the studies of the multicomponent reaction of 5-hydroxy-2-methyl-4H-pyran-4-one with carbonyl compounds and Meldrum's acid. General methods for the synthesis of 6-methyl-3,4-dihydropyrano[3,2-b]pyran-2,8-diones, 3-(3-hydroxy-6-methyl-4-oxo-4H-pyran-2-yl)propanoic acid amides and esters, as well as 7-oxo-7H-furo[3,2-b]pyran-3-ylacetic acids were elaborated. An efficient synthesis of spiro-condensed dihydropyranones containing 5-hydroxy-2-methyl-4H-pyran-4-one fragment was developed.

Investigation of the multicomponent reaction of 5-hydroxy-2-methyl-4 h -pyran-4-one with carbonyl compounds and meldrum's acid

Procedures were developed for the synthesis of substituted bis(2,5-dimethyl-3-thienyl)furans based on 1,2-bis(2,5-dimethyl-3-thienyl)-2-hydroxyethanone. Dithienylethene structures in which the ethene fragment is involved in the furan or furopyrimidine system possess photochromic properties and their open forms exhibit fluorescence.

Photochromic dihetarylethenes. 11. Synthesis and photochromic properties of diarylethenes containing furan or furopyrimidine bridges

A novel, convenient method has been developed for the synthesis of 1,2-bis(2,5-dimethyl-3-thienyl)ethanedione, from which were prepared 5,6-bis(2,5-dimethyl-3-thienyl)-1,2,4-triazines (analogs of the photochromic 1,2-diarylethenes). The principial possibility of using 1,2,4-triazines obtained as photochromic agents was investigated.

Arkady A. Dudinov

Papers

Photochromic dihetarylethenes. 7. Synthesis of bis(thienylazoles), photochromic analogs of diarylethenes

Investigation of the multicomponent reaction of 5-hydroxy-2-methyl-4 h -pyran-4-one with carbonyl compounds and meldrum's acid

Photochromic dihetarylethenes. 11. Synthesis and photochromic properties of diarylethenes containing furan or furopyrimidine bridges

Synthesis of Substituted 1,2,4-Triazines Based on 1,2-Bis(2,5-dimethyl-3-thienyl)ethanedione

Synthesis of substituted benzofuran-3-ylacetic acids based on three-component condensation of polyalkoxyphenols, arylglyoxals and Meldrum's acid