Development of xanthene dyes containing arylacetylenes: The role of acetylene linker and substituents on the aryl group

Fluorescent dyes possessing a variety of arylacetylenes at the 9-position of a xanthene skeleton were synthesized and their optical properties were investigated. The π system effectively expanded over the xanthene skeleton and the aryl group through the triple bond. Starting from the emission wavelength (λ_em) of 9-methyl xanthene 20 in basic DMSO solution at 536?nm, the emission wavelengths gradually shifted to the red region for methylacetylene 17 (λ_em?=?600?nm), phenylacetylene 5 (λ_em?=?636?nm), and p-CF₃-phenylacetylene 11 (λ_em?=?660?nm). On the basis of these data, we estimated the substituent effects for the red shift on the emission wavelength and rationally explained the results by DFT calculations. Furthermore, potential applicability of these fluorescent dyes to cell staining was exemplified.     

Selective synthesis of 1,4,5-trisubstituted imidazoles from α-imino ketones prepared by N-heterocyclic-carbene-catalyzed aroylation

An alternative synthetic route to 1,4,5-trisubstituted imidazoles from α-imino ketone, which can be prepared from imidoyl chlorides and aromatic aldehydes via N-heterocycle carbene-catalyzed aroylation was developed. This methodology consists of simple transformations, allowing a rapid access to imidazole derivatives with various aryl substituents at the desired positions.     

Fluctuating Carbonaceous Networks with a Persistent Molecular Shape: A Saddle‐Shaped Geodesic Framework of 1,3,5‐Trisubstituted Benzene (Phenine)

A saddle‐shaped macromolecule has been synthesized. The molecule was designed as a geodesic saddle with 1,3,5‐trisubstituted benzene (named phenine) as the fundamental unit. The phenines were woven into a polygonal framework that was composed of 168 sp²‐hybridized carbon atoms. The saddle‐shaped structure with unique symmetry showed atypical conformational changes. The biaryl linkages in this molecule had a small energy barrier for rotation, and these structural fluctuations resulted in seven ¹H NMR resonances representing 84 aromatic hydrogen atoms. Nevertheless, the overall saddle shape of the molecule was persistent, and the “up” and “down” orientations of phenine moieties circulated to give average ¹H resonances. The structural characteristics of this molecule, including the anomalous entropy‐driven dimerization, may deepen our understanding of defect‐rich graphitic sheets.     

Metal‐ and Oxidant‐Free Alkenyl C−H/Aromatic C−H Cross‐Coupling Using Electrochemically Generated Iodosulfonium Ions

A three‐step transformation consisting of 1) addition of electrochemically generated iodosulfonium ions to vinylarenes to give (1‐aryl‐2‐iodoethoxy)sulfonium ions, 2) nucleophilic substitution by subsequently added aromatic compounds to give 1,1‐diaryl‐2‐iodoethane, and 3) elimination of HI with a base to give 1,1‐diarylethenes was developed. The transformation serves as a powerful metal‐ and chemical‐oxidant‐free method for alkenyl C?H/aromatic C?H cross‐coupling.     

A Catalyst‐Free Amination of Functional Organolithium Reagents by Flow Chemistry

Reported is the electrophilic amination of functional organolithium intermediates with well‐designed aminating reagents under mild reaction conditions using flow microreactors. The aminating reagents were optimized to achieve efficient C?N bond formation without using any catalyst. The electrophilic amination reactions of functionalized aryllithiums were successfully conducted under mild reaction conditions, within 1 minute, by using flow microreactors. The aminating reagent was also prepared by the flow method. Based on stopped‐flow NMR analysis, the reaction time for the preparation of the aminating reagent was quickly optimized without the necessity of work‐up. Integrated one‐flow synthesis consisting of the generation of an aryllithium, the preparation of an aminating reagent, and their combined reaction was successfully achieved to give the desired amine within 5 minutes of total reaction time.     

Total Synthesis and Biological Evaluation of Siladenoserinol A and its Analogues

The total synthesis of siladenoserinol A, an inhibitor of the p53–Hdm2 interaction, has been achieved. AuCl₃‐catalyzed hydroalkoxylation of an alkynoate derivative smoothly and regioselectively proceeded to afford a bicycloketal in excellent yield. A glycerophosphocholine moiety was successfully introduced through the Horner–Wadsworth–Emmons reaction using an originally developed phosphonoacetate derivative. Finally, removal of the acid‐labile protecting groups, followed by regioselective sulfamate formation of the serinol moiety afforded the desired siladenoserinol A, and benzoyl and desulfamated analogues were also successfully synthesized. Biological evaluation showed that the sulfamate is essential for biological activity, and modification of the acyl group on the bicycloketal can improve the inhibitory activity against the p53–Hdm2 interaction.     

One‐pot Annulation for Biaryl‐fused Monocarba‐closo‐dodecaborate through Aromatic B−H Bond Disconnection

We have developed a one‐pot annulation reaction of monocarba‐closo‐dodecaborate with cyclic diaryliodonium salts to afford biaryl‐fused derivatives. Aryl functionalities are introduced at both the 1‐carbon and unreactive ortho‐boron vertices of the “σ‐aromatic” carborane cage without the need for pre‐functionalization. DFT calculations revealed that the palladium‐catalyzed C?B bond‐formation step in this process proceeds through a concerted metalation–deprotonation (CMD)‐type pathway for the B?H bond disconnection on the aromatic cage, though such bonds are generally regarded as hydridic.     

Magnetic moments of proton drip-line nuclei13O and9C

The magnetic moments of the proton drip-line nuclei¹³O(I = 3/2^–,T _1/2 = 8.6 ms) and 9C(I = 3/2^–,T _1/2 = 126 ms) have been determined for the first time through the combined techniques of polarized radioactive nuclear beams and-NMR detection. The observed magnetic moments are ¦(¹³O)¦ = 1.3891 ±0.0003 _N and ¦(⁹C)¦ = 1.3914 ±0.0005 _N. Spin expectation values are deduced to be 0.76 and 1.44 for¹³O and⁹C, respectively. While the of¹³O is consistent with the systematics from isospinT= 1/2 mirror pairs, the of⁹C is unusually large, even far larger than the single particle value, = 1.