Efficient Synthesis of Polycyclic γ-Lactams by Catalytic Carbonylation of Ene-Imines via Nickelacycle Intermediates

The nickel(0)-catalyzed carbonylative cycloaddition of 1,5- and 1,6-ene-imines with carbon monoxide (CO) is reported. Key to this reaction is the efficient regeneration of the catalytically active nickel(0) species from nickel carbonyl complexes such as [Ni(CO)₃L]. A variety of tri- and tetracyclic γ-lactams were thus prepared in excellent yields with 100 % atom efficiency. Preliminary results on asymmetric derivatives promise potential in the synthesis of enantioenriched polycyclic γ-lactams.     

Isoregic Thienylene‐Phenylene Polymers: The Effects of Structural Variation and Application to Photovoltaic Devices

Isoregic conjugated polymers composed of thiophene and dialkoxybenzene units were designed to harvest incident light in the mid‐visible energy range (band gap of 2.1 eV). Poly(1,4‐bis(2‐thienyl)‐2,5‐diheptoxybenzene) (PBTB(OC₇H₁₅)₂) and poly(1,4‐bis(2‐thienyl)‐2,5‐didodecyloxybenzene) (PBTB(OC₁₂H₂₅)₂) have shown significant photovoltaic performance as an electron donor when used in tandem with the electron acceptor [6, 6]‐phenyl C₆₁‐butyric acid methyl ester (PCBM) in bulk hetero‐junction photovoltaic devices. Photovoltaic devices incorporating PBTB(OC₇H₁₅)₂ and PCBM have shown AM1.5 efficiencies of ～0.6% with a short circuit current density of 2.5 mA/cm², an open circuit voltage of 0.74 V, and a fill factor of 0.32. Incident Photon‐to‐Current Efficiency (IPCE) of the device was found to be ca. 16% at 410 nm. In order to examine the relationship between the molecular structure of the polymers and their electronic energy levels, and to correlate this with photovoltaic performance, optoelectronic and electrochemical results are discussed in relation to the I‐V characteristics of the devices. Additionally, a computer‐aided simulation is used to gain further insight into the effect of polymer structure on the energetic relationships in the bulk heterojunction devices.     

In Silico Design of Heteroaromatic Half‐Sandwich RhI Catalysts for Acetylene [2+2+2] Cyclotrimerization: Evidence of a Reverse Indenyl Effect

A mechanistic density functional theory study of acetylene [2+2+2] cyclotrimerization to benzene catalyzed by Rh^I half metallocenes is presented. The catalyst fragment contains a heteroaromatic ligand, that is, the 1,2‐azaborolyl (Ab) or the 3a,7a‐azaborindenyl (Abi) anions, which are isostructural and isoelectronic to the hydrocarbon cyclopentadienyl (Cp) and indenyl (Ind) anions, respectively, but differ from the last ones on having two adjacent carbon atoms replaced with a boron and a nitrogen atom. The better performance of either the classic hydrocarbon or the heteroaromatic catalysts is found to depend on the different mechanistic paths that can be envisioned for the process. The present analyses uncover and explain general structure–reactivity relationships that may serve as rational design principles. In particular, we provide evidence of a reverse indenyl effect.