Copper‐Catalyzed Stereoselective Aminoboration of Bicyclic Alkenes

A copper‐catalyzed aminoboration of bicyclic alkenes, including oxa‐ and azabenzonorbornadienes, has been developed. With this method, amine and boron moieties are simultaneously introduced at an olefin with exo selectivity. Subsequent stereospecific transformations of the boryl group can provide oxygen‐ and nitrogen‐rich cyclic molecules with motifs that may be found in natural products or pharmaceutically active compounds. Moreover, a catalytic asymmetric variant of this transformation was realized by using a copper complex with a chiral bisphosphine ligand, namely (R,R)‐Ph‐BPE.     

Copper‐Catalyzed Intramolecular Oxidative Amination of Unactivated Internal Alkenes

A copper‐catalyzed oxidative amination of unactivated internal alkenes has been developed. The Wacker‐type oxidative alkene amination reaction is traditionally catalyzed by a palladium through a mechanism involving aminopalladation and β‐hydride elimination. Replacing the precious and scarce palladium with a cheap and abundant copper for this transformation has been challenging because of the difficulty associated with the aminocupration of internal alkenes. The combination of a simple copper salt, without additional ligand, as the catalyst and Dess–Martin periodinane as the oxidant, promotes efficiently the oxidative amination of allylic carbamates and ureas bearing di‐ and trisubstituted alkenes leading to oxazolidinones and imidazolidinones. Preliminary mechanistic studies suggested a hybrid radical–organometallic mechanism involving an amidyl radical cyclization to form the key C?N bond.     

Ring Opening of Pymisyl‐Protected Aziridines with Organocuprates

The pyrimidine‐2‐sulfonyl (pymisyl) group is introduced as a new protecting group that can be used to activate aziridines towards ring opening. It is readily introduced and removed under mild conditions. Regioselective ring opening of pymisyl‐protected 2‐methyl‐aziridine with organocuprates gives the corresponding sulfonamides in high yields, and the pymisyl group can subsequently be removed upon treatment with a thiolate. The versatility of this new nitrogen protecting group is illustrated with a new synthesis of Selegiline, a monoamine oxidase‐B inhibitor marketed for the treatment of Parkinson’s disease.     

Lead-oriented synthesis: a new opportunity for synthetic chemistry

The pharmaceutical industry remains solely reliant on synthetic chemistry methodology to prepare compounds for small-molecule drug discovery programmes. The importance of the physicochemical properties of these molecules in determining their success in drug development is now well understood but we present here data suggesting that much synthetic methodology is unintentionally predisposed to producing molecules with poorer drug-like properties. This bias may have ramifications to the early hit- and lead-finding phases of the drug discovery process when larger numbers of compounds from array techniques are prepared. To address this issue we describe for the first time the concept of lead-oriented synthesis and the opportunity for its adoption to increase the range and quality of molecules used to develop new medicines.     

强激光反射镜基体材料的热畸变特性有限元分析

利用有限元方法数值模拟了单晶硅（Si）、铜（Cu）、钨(W)、氧化铍(BeO)等镜体材料的热畸变特性。结果表明：当入射激光功率为2 kW、镜面反射率为93%、光斑直径为17 mm、激光照射时间为10 s时,四种材料基板的中心最大热变形分别为0.984,3.32,1.55,1.88 μm。相比之下,Si镜的热变形最小,是比较理想的镜体材料;Cu镜的热变形最大;W和BeO两种材料的镜热变形介于Si镜和Cu镜之间,具有较高的强度和硬度,抗破坏能力较强。     

An Iron Complex with an Unsupported Fe–Fe Bond

Full metal bonding : The reduction of a six‐coordinate, mononuclear Werner‐type iron(II) complex (see scheme) resulted in the isolation of a compound with an extraordinarily rare, unsupported Fe–Fe bond having an experimental Fe–Fe distance of 2.6869(6) Å and a calculated bond order of 0.5.

     

Enantioselective Organocatalytic Diels–Alder Trapping of Photochemically Generated Hydroxy‐o‐Quinodimethanes

The photoenolization/Diels–Alder strategy offers straightforward access to synthetically valuable benzannulated carbocyclic products. This historical light‐triggered process has never before succumbed to efforts to develop an enantioselective catalytic approach. Herein, we demonstrate how asymmetric organocatalysis provides simple yet effective catalytic tools to intercept photochemically generated hydroxy‐o‐quinodimethanes with high stereoselectivity. We used a chiral organic catalyst, derived from natural cinchona alkaloids, to activate maleimides toward highly stereoselective Diels–Alder reactions. An unconventional mechanism of stereocontrol is operative, wherein the organocatalyst is actively involved in both the photochemical pathway, by leveraging the formation of the reactive photoenol, and the stereoselectivity‐defining event.     

Bi(NO3)3 · 5H2O mediated synthesis of 4,4′-diaminotriarylmethane leuco malachite compounds under solvent-free conditions

In this report, we described the synthesis and characterization of a variety of diaminotriarylmethane derivatives with dimethylamino functional groups. These compounds were synthesized by the tandem regio-selective electrophilic aromatic substitution reaction of N,N-dimethylaniline with aryl aldehydes to form the corresponding diaminotriarylmethane compounds. In our strategy, Bi(NO₃)₃ was used as a catalyst under solvent free conditions to afford the desired products in good to excellent yields.      

From Molecules to Materials: Computational Design of N‐Containing Porous Aromatic Frameworks for CO2 Capture

Porous aromatic frameworks (PAFs) are novel materials with diamond topology. With the aim of enhancing their CO₂ capture and storage capacity and investigating the effect of nitrogen and/or ‐COOH decorations on CO₂ adsorption in PAFs, a series of N‐containing PAFs were designed based on ab initio results. The interaction energies (E_int) between CO₂ and each six‐membered ring were calculated at the B2PLYP‐D2/def2‐TZVPP level, then the six‐membered rings with high CO₂‐binding affinity were selected and used in the PAFs. To explore the performance of the designed PAFs, the CO₂ uptake, selectivity of CO₂ over CH₄, H₂, and N₂, and the E_int value of CO₂ in PAFs were investigated by using grand canonical Monte Carlo (GCMC) simulations and ab initio calculations. This work shows that pyridine with one nitrogen atom can provide a strong physisorption site for CO₂, whereas more nitrogen atoms in heterocycles will reduce the interaction, especially at relatively low pressure. PAFs with ?COOH groups show high CO₂ capacity. Our work provides an efficient way to understand the adsorption mechanism and a supplemental approach to experimental work.     

Construction of Chiral Tri‐ and Tetra‐Arylmethanes Bearing Quaternary Carbon Centers: Copper‐Catalyzed Enantioselective Propargylation of Indoles with Propargylic Esters

Copper‐catalyzed enantioselective propargylation of indoles with propargylic esters and sequential Huisgen cycloaddition with azides lead to the construction of chiral triarylmethanes, bearing a quaternary carbon center, with high to excellent enantioselectivities. The result described herein can be used in the enantioselective preparation of a tetraarylmethane.