Thiazolocatechol: Electron-Withdrawing Catechol Anchoring Group for Dye-Sensitized Solar Cells

Anchoring groups adopting a five-membered bidentate chelating are attractive to realize high power conversion efficiency (η) and long-term durability in dye-sensitized solar cells (DSSCs). In this regard, we chose catechol as an anchoring group that can adopt the chelating. However, the DSSCs with catechol-based sensitizers have never exceeded an η-value of 2 %. These poor photovoltaic performances may be associated with the electron-donating ability of the hydroxy groups in catechol. Considering these, we envisioned that fusing an electron-withdrawing thiazole moiety with a catechol anchoring group would improve its photovoltaic performance. Herein, we report a push-pull porphyrin sensitizer ZnPTC with a thiazolocatechol anchoring group. The DSSC with ZnPTC exhibited η=4.87 %. This value is the highest ever reported for catechol-anchor based DSSCs. Meanwhile, the long-term cell durability was not improved, although the robust anchoring properties were attained under harsh conditions.     

Structure–activity relationship of dihydroimidazo-, dihydropyrimido,tetrahydrodiazepino-[2,1-b]-thiazoles,and -benzothiazoles as an acylation catalyst

Cyclic isothioureas 1, 2, 3, and 4 were synthesized through a four-step procedure from the corresponding ortho-bromoanilines 10 via Pd- or Cu-catalyzed cyclization–benzothiazole formation. Nonbenzo analogues 7, 8, and 9 were synthesized by a condensation reaction of cyclic thioureas 15 and α-bromoacetophenones 14. Investigations of the acylation reactions of 1-phenylethanol with acid anhydrides in the presence of these cyclic isothiourea catalysts revealed their structure–activity relationships. Remarkable electronic effects resulting from substituent(s) on a benzo or phenyl moiety and the influence of the size of the annulating ring were observed. Introduction of an electron-donating substituent(s) enhanced the reaction rate. A few substitution effects on chiral catalysts of type 3 and 7 were also studied.     

Synthesis, Reactivity, and Spectroscopic Properties of meso-Triaryl-5-oxaporphyrins

[meso-Triaryl-21,23-didehydro-23H-5-oxaporphyrinato](trifluoroacetato)zinc(II) was prepared by the reaction of meso-triarylbilindione with acetic anhydride and zinc acetate, and it was isolated as a trifluoroacetate salt. The X-ray crystallographic study demonstrated that the trifluoroacetate anion was coordinated to the zinc ion. [21,23-Didehydro-10,15,20-tris(4-methoxycarbonylphenyl)-23H-5-oxaporphyrinato](trifluoroacetato)zinc(II) 3a was dissolved in various organic solvents such as toluene, chloroform, diethyl ether, ethyl acetate, acetone, acetonitrile, methanol, DMSO, and DMF, although it readily reacted with alcohols and DMF to yield linear tetrapyrroles. The solubility of 3a in toluene was 4.2 ± 0.1 g dm(-3) at room temperature. 3a showed characteristic UV-vis absorption at 649 nm and fluorescence emission at 657 nm in chloroform. The fluorescence quantum yields of 3a, [21,23-didehydro-10,15,20-triphenyl-23H-5-oxaporphyrinato](trifluoroacetato)zinc(II) (3c), and [21,23-didehydro-10,15,20-tris(4-methoxyphenyl)-23H-5-oxaporphyrinato](trifluoroacetato)zinc(II) (3b) were 0.071, 0.071, and 0.050, respectively. Reaction of 3a with EtOH afforded the zinc complex of 19-ethoxybilinone, and it proceeded 2 orders of magnitude faster than that of [β-octaalkyl-21,23-didehydro-23H-5-oxaporphyrinato]zinc(II). The reaction with alcohols was sensitive to steric bulk of the alcohols; the rate of reaction with i-PrOH was 2700 times faster than that of t-BuOH at 303 K. The reaction of [meso-triaryl-21,23-didehydro-23H-5-oxaporphyrinato]zinc(II) with water proceeded 3 orders of magnitude slower than that with EtOH.     

Palladium(0)-catalyzed cyclization of electron-deficient enynes and enediynes

In the presence of a Pd(0) precatalyst, Pd2(bq)2(nbe)2 or Pd2(dba)3, 1,6-enyne esters were heated in refluxing benzene to give cyclodimers as single regioisomers. On the other hand, the combination of the Pd(0) precatalyst and triphenyl phosphite gave rise to various cycloisomerization products depending on the substitution pattern of the enyne esters. Six-membered ring cycloisomerization products were predominantly obtained from enyne esters bearing methallyl or 2-phenyl-2-propenyl moieties, while other enyne esters afforded normal five-membered ring cycloisomerization products. Intramolecular [2 + 2 + 2] cyclocotrimerization of enediyne esters also proceeded in the presence of the Pd(0) precatalyst and triphenylphosphine to give fused cyclohexadienes.     

The optimization for cyclization reaction of 2-(2-carbomethoxyethynyl)aniline derivatives and formal synthesis of pyrroloquinoline quinone and its analogue utilizing a sequential coupling-cyclization reaction

The reaction conditions for the Pd-catalyzed cyclization reaction of 2-(2-carbomethoxyethynyl)aniline derivatives were investigated. The amounts of Pd(PPh₃)₄, methyl propiolate, and ZnBr₂ could be significantly reduced compared with those reported in our preliminary publication by careful tuning of the solvent and the reaction temperature. In addition to the above results, formal syntheses of pyrroloquinoline quinone (PQQ) and its analogue from 2-amino-5-nitrophenol using a Pd-complex-catalyzed sequential coupling-cyclization reaction between methyl propiolate and 2-iodoaniline derivatives are described.     

Total synthesis of janadolide

The first total synthesis of janadolide, a new cyclic polyketide-peptide hybrid possessing a tert-butyl group, is described. The synthesis of an unsaturated hydroxycarboxylic acid was effected via the lithiation of vinyl iodide followed by addition to a Weinreb amide with a tert-butyl group and stereoselective 1,2-reduction. The cyclic structure was constructed by macrolactamization at the amide bond between the proline moiety and fatty acid moiety.     

Fragmentation selectivity in electron impact ionization mass spectra of substituted dimethoxybenzenes

Several 1-X-sabstitirted-3-methoxy-4-trideuteromethoxybenzens were synthesized and their electron impact ionization mass spectra were measured with an ionizing energy of 20 eV. From the peak intensity ratio of [M ? CD₃ ] and [M ? CH₃] the fragmentation-directing ability of the substituent X was evaluated. The most powerful group was found to be NH₂, which expelled a methoxy methyl group only from its para position. The CH₃ group and four halogen atoms, F, Cl, Br and I, exerted a moderate effect Electron-withdrawing groups such as NO₂, CHO and CN had only a little influence on the fragmentation selectivity. These results were interpreted in terms of the effect of X on the distribution of both the unpaired electron and the positive charge in the molecular ion.     

Diorganostannylenes : III. Formation of dimethylstannylene from 1,1-dimethyl-2,3,4,5-tetraphenyl-1-stannacyclopentadiene and acetylenes

Dimethylstannylene, (CH₃)₂Sn:, was formed transiently in the reaction of 1,1-dimethyl-2,3,4,5-tetraphenyl-1-stannacyclopentadiene (stannole) with dimethyl acetylenedicarboxylate or phenylacetylene. When this reaction was carried out in the presence of n-butyl bromide, dimethylstannylene inserted into the CBr bond of n-butyl bromide to give n-butyldimethyltin bromide in 12% yield, but most of the dimethylstannylene was captured by dimethyl acetylenedicarboxylate to give a complex. The complex was also produced in the photolytic reaction of the dimethyltin polymer, [(CH₃)₂Sn]_m, with dimethyl acetylenedicarboxylate. With phenylacetylene, dimethylstannylene did not give a similar complex, but polymerized to give the dimethyltin polymer.     

Palladium(0)-catalyzed intramolecular [2+2+2] alkyne cyclotrimerizations with electron-deficient diynes and triynes

In the presence of 2.5 mol % of [Pd(2)(dba)(3)] (dba=dibenzylideneacetone) and 5 mol % of PPh(3), nearly equimolar amounts of dimethyl nona-2,7-diyne-1,9-dioate derivatives (diyne diesters) and dialkyl acetylenedicarboxylates were allowed to react in toluene at 110 degrees C to afford [2+2+2] cycloadducts in moderate-to-good yields. Similarly, dimethyl trideca-2,7,12-triyne-1,13-dioate derivatives (triyne diesters) were catalytically transformed into phthalic acid ester analogues in excellent yields. To gain insight into the mechanism of these intramolecular alkyne cyclotrimerizations, stoichiometric reactions of [Pd(2)(dba)(3)] with a diyne diester and a triyne diester bearing ether tethers were conducted in acetone at room temperature to furnish an oligomeric bicyclopalladacyclopentadiene and a Pd(0) triyne complex, respectively. The structures of these novel complexes were unequivocally determined by Xray structure analysis. The isolated triyne complex was heated at 50 degrees C or treated with PPh(3) in acetone at room temperature to afford the arene product. Furthermore, the same complex catalyzed the triyne cyclization with or without PPh(3).