Throw your hat in the ring : A highly diastereoselective synthesis of the ABC rings of (?)‐norzoanthamine has been achieved starting from the (?)‐Hajos–Parrish ketone (see scheme). Three asymmetric quaternary carbon centers on the C ring were constructed by a 1,4‐addition, and an intramolecular Diels–Alder reaction provided a trans‐decalin scaffold on the AB rings.
On solid ground : A new solid‐phase synthesis of N‐linked glycans featuring 1) highly stereoselective β‐mannosylation and microfluidic α‐sialylation and 2) efficient glycosylation of the N‐phenyltrifluoroacetimidate units on JandaJel resin is reported. Reagent concentration effects by a fluorous solvent are effectively applied, and the use of these methods results in the first synthesis of a sialic acid containing complex‐type N‐glycan on a solid support.
Let K be either the rational number field
\Bbb Q{\Bbb Q} or an imaginary quadratic field. We give irrationality results for the number q = ?n=1¥rn/(qn-rl)\theta=\sum_{n=1}^{\infty}{r^n}/(q^n-r^l), where q (∣q∣ > 1) is an integer in K, r∈ K× (∣r∣ < ∣q∣), and
1 £ l ? \Bbb Z1\le l\in{\Bbb Z} with qn ≠ rl (n ≥ 1). 相似文献
Contrary to 4,4'-dipyridinium (i.e., archetypal methyl viologen), which is reduced by two single-electron transfers (stepwise reduction), the 4,1'-dipyridinium isomer (so-called "head-to-tail" isomer) undergoes two electron transfers at apparently the same potential (single-step reduction). A combined theoretical and experimental study has been undertaken to establish that the latter electrochemical behavior, also observed for other polyarylpyridinium electrophores, is due to potential compression originating in a large structural rearrangement. Three series of branched expanded pyridiniums (EPs) were prepared: N-aryl-2,4,6-triphenylpyridiniums (Ar-TP), N-aryl-2,3,4,5,6-pentaphenylpyridiniums (Ar-XP), and N-aryl-3,5-dimethyl-2,4,6-triphenylpyridinium (Ar-DMTP). The intramolecular steric strain was tuned via N-pyridinio aryl group (Ar) phenyl (Ph), 4-pyridyl (Py), and 4-pyridylium (qPy) and their bulky 3,5-dimethyl counterparts, xylyl (Xy), lutidyl (Lu), and lutidylium (qLu), respectively. Ferrocenyl subunits as internal redox references were covalently appended to representative electrophores in order to count the electrons involved in EP-centered reduction processes. Depending on the steric constraint around the N-pyridinio site, the two-electron reduction is single-step (Ar = Ph, Py, qPy) or stepwise (Ar = Xy, Lu, qLu). This steric switching of the potential compression is accurately accounted for by ab initio modeling (Density Functional Theory, DFT) that proposes a mechanism for pyramidalization of the N(pyridinio) atom coupled with reduction. When the hybridization change of this atom is hindered (Ar = Xy, Lu, qLu), the first reduction is a one-electron process. Theory also reveals that the single-step two-electron reduction involves couples of redox isomers (electromers) displaying both the axial geometry of native EPs and the pyramidalized geometry of doubly reduced EPs. This picture is confirmed by a combined UV-vis-NIR spectroelectrochemical and time-dependent DFT study: comparison of in situ spectroelectrochemical data with the calculated electronic transitions makes it possible to both evidence the distortion and identify the predicted electromers, which play decisive roles in the electron-transfer mechanism. Last, this mechanism is further supported by in-depth analysis of the electronic structures of electrophores in their various reduction states (including electromeric forms). 相似文献
Desmosine, a crosslinking amino acid of elastin, is an attractive biomarker for diagnosis of chronic obstructive pulmonary disease (COPD). In this study, the first total synthesis of (+)-desmosine was achieved in 11% overall yield in 13 steps utilizing stepwise and regioselective Sonogashira cross-coupling reactions. 相似文献
Multiwalled carbon nanotubes (MWCNTs) were incorporated into amorphous dye-doped titania gel by the sol?Cgel method at room temperature. The working electrodes were prepared by coating the ITO glass with the sol?Cgel titania precursor containing the dye and MWCNTs. The photoelectric conversion properties of the electrodes were examined by simple spectroscopic and electric measurements. The photocurrent spectrum originated from the absorption of the dye. The short circuit photocurrent was enhanced by adding a small amount of MWCNTs evenly to the amorphous dye-doped titania gel. The open circuit voltage was due to the semiconducting characteristics property of the titania gel. The experimental results indicated the electron transport from the dye excited states to the MWCNTs through the titania gel. The MWCNTs functioned as bridges between the titania and ITO. Steam treatment of the titania gel electrodes significantly increased the photoelectric performance due to crystallization of the titania and enhancement of the dye?Ctitania interaction forming the chelate complex on the titania particle surface. 相似文献
The enantioselective reduction of ketones was accomplished by borane in the presence of pyrazole derivatives, particularly 2‐methoxymethyl‐3‐phenyl‐1‐menthopyrazole (8). The catalysis of zinc chloride makes it possible to lower the reaction temperature below 0 °C, and to promote enantioselectivity. 相似文献
A recent intriguing finding that a helical network arrangement forms the bicontinuous cubic phase is attracting great attention for the possibility of new routes to asymmetric synthesis by achiral molecules. However, the design of the molecular structure for the cubic phase is still unrevealed. In this work, a nonsymmetric core molecule with larger naphthalene and smaller benzene moieties at each side of the central linkage and the same disiloxanyldecyloxy terminal at both terminals is shown to be the first example of molecule forming both single-layered and double-layered core assembly modes in the Ia3d phase as a single molecule system. The molecule forms the former mode at high temperatures as a thermodynamically stable phase, similarly to the symmetric naphthalene core system, whereas, on cooling below a temperature (∼350 K), a metastable Ia3d phase forms a double-layered core state down to room temperature, which is common to the benzene core system. As another effect of the nonsymmetric core, the cubic phase is maintained at room temperature for more than 100 days with slight distortion. Infrared spectral studies and quantum chemical calculations suggested the easy transformation between the two core assembly modes. The core nonsymmetry can be a versatile fine-tuning of the core assembly mode and phase stability for the cubic phase molecules. 相似文献