Dibenzoarsepins: Planarization of 8π‐Electron System in the Lowest Singlet Excited State

Dibenzo[b,f]arsepins possessing severely distorted cores compared to those of other heteropins were synthesized. These derivatives exhibited dual photoluminescence in the green‐to‐red region (500–700 nm) and the near‐ultraviolet region (<380 nm), which could be attributed to the planarization of the arsepin core in the lowest singlet excited (S₁) state. The computational approach for the assessment of the aromatic indices revealed that the dibenzoarsepins studied show aromaticity (8π system) in the S₁ states in line with Baird's rule. The lone pair electrons of the arsenic atoms play a crucial role in the aromaticity in the S₁ states.     

An Unprecedented Cyclization Mechanism in the Biosynthesis of Carbazole Alkaloids in Streptomyces

Carquinostatin A (CQS), a potent neuroprotective substance, is a unique carbazole alkaloid with both an ortho‐quinone function and an isoprenoid moiety. We identified the entire gene cluster responsible for CQS biosynthesis in Streptomyces exfoliatus through heterologous production of CQS and gene deletion. Biochemical characterization of seven CQS biosynthetic gene products (CqsB1–7) established the total biosynthetic pathway of CQS. Reconstitution of CqsB1 and CqsB2 showed that the synthesis of the carbazole skeleton involves CqsB1‐catalyzed decarboxylative condensation of an α‐hydroxyl‐β‐keto acid intermediate with 3‐hydroxybutyryl‐ACP followed by CqsB2‐catalyzed oxidative cyclization. Based on crystal structures and mutagenesis‐based biochemical assays, a detailed mechanism for the unique deprotonation‐initiated cyclization catalyzed by CqsB2 is proposed. Finally, analysis of the substrate specificity of the biosynthetic enzymes led to the production of novel carbazoles.     

Radial breathing modes of single-walled carbon nanotubes in resonance Raman spectra at high temperature and their chiral index assignment

Radial breathing modes (RBMs) in resonance Raman spectra from single-walled carbon nanotubes (SWCNTs) on a SiO₂/Si (0 0 1) substrate are studied between 25 and 720 °C. A change in the relative intensity of each RBM peak with temperature is observed, which originates from the temperature dependence of the resonance condition of nanotubes. For 25 °C, each RBM peak is reasonably assigned on the basis of data in the literature [J. Maultzsch, H. Telg, S. Reich, F. Hennrich, C. Thomsen, Phys. Rev. B 72 (2005) 205438]. By taking into account the temperature-dependent behavior of the relative intensity of the RBM peaks, each RBM peak is successfully assigned even for 720 °C. It is found that most of the observed RBM peaks for a laser excitation energy of E_exc = 1.96 eV are from chiral SWCNTs. These results make it possible to discuss further details of the chirality-dependent growth behavior observed for in situ Raman spectroscopy.     

Catalytic Alkynylation of Polyfluoroarenes by Amide Base Generated In Situ

We herein demonstrate that the amide base generated in situ from CsF and N(TMS)₃ catalyzes the deprotonative coupling reactions of terminal alkynes with polyfluoroarenes, wherein mono- and dialkynylations occur efficiently for penta- and hexafluorobenzenes, respectively. Tetraalkynylated products could also be synthesized from dialkynylated compounds.     

Phosphine‐Catalyzed anti‐Carboboration of Alkynoates with 9‐BBN‐Based 1,1‐Diborylalkanes: Synthesis and Use of Multisubstituted γ‐Borylallylboranes

Trialkylphosphine organocatalysis has enabled the regioselective anti‐carboboration of alkynoates with 9‐BBN‐based 1,1‐diborylalkanes to produce secondary allylboranes with β‐alkoxycarbonyl and γ‐boryl substituents. The utility of the densely functionalized allylboranes was demonstrated by the highly diastereoselective allylation of N‐(trimethylsilyl)aldimines to produce homoallylamines containing tertiary allylborane and acrylate moieties.     

Diastereoselective synthesis of useful building blocks by crotylation of beta-branched alpha-methylaldehydes with potassium crotyltrifluoroborates

The diastereoselective construction of stereotriads having consecutive methyl, hydroxy, and methyl substituents was realized by the substrate-controlled crotylation of beta-branched alpha-methylaldehydes with potassium crotyltrifluoroborates. Especially, crotylation of 2-(1,3-dithian-2-yl)propanal with potassium ( E)-crotyltrifluoroborate afforded, in good yield and with excellent diastereoselectivity, a useful building block that has different and potential functional groups on both ends.