Internally Reuse Waste: Catalytic Asymmetric One‐Pot Strecker Reaction of Fluoroalkyl Ketones,Anilines and TMSCN by Sequential Catalysis

We report a highly enantioselective one‐pot facile synthesis of fluorinated C^α‐tetrasubstituted amino nitriles from α‐fluoroalkyl α‐aryl ketones, anilines, and TMSCN through a sequential p‐TsOH catalyzed ketimine formation and chiral bifunctional tertiary amine mediated asymmetric Strecker reaction. This one‐pot approach has two important advantages. First, it greatly improves the overall yield of the synthesis of chiral C^α‐tetrasubstituted fluorinated aminonitriles from ketones, because the purification of α‐fluorinated ketimines by column chromatography suffers from great yield loss. Second, it represents the first example of asymmetric tandem reactions that can simultaneously reuse the by‐product and catalyst from the upstream step as a promoter and an additive to improve the reactivity and enantioselectivity of the subsequent catalytic enantioselective reaction, respectively. It could utilize the by‐product H₂O generated in‐situ from the ketimine formation step to activate TMSCN to form HCN, and concurrently reuse the remaining p‐TsOH acid as an additive to improve enantioselectivity.     

Inside Cover: Upgrading CO2 by Incorporation into Urethanes through Silver‐Catalyzed One‐Pot Stepwise Amidation Reaction (Chin. J. Chem. 2/2018)

The inside cover picture shows an outline of significant advances on exhaust gas e.g. sustainable CO₂ recycling into urethanes via effective and renewable silver catalysis. Through one‐pot two‐step stepwise reaction of propargylic alcohols, CO₂, and various amines, a wide range of urethanes are obtained in excellent yields and selectivity together with unprecedented high TON and TOF value under mild conditions. Here, robust catalyst is compared to Magician's hand for its versatility in organic synthesis, and the picture indicates the meanings of greenness and transformation. More details are discussed in the article by Zhang et al. on page 147–152.

     

Back Cover: Asymmetric Synthesis of the Ring A Substructure of Genkwadane A (Chin. J. Chem. 9/2018)

The back cover picture shows Genkwadane A was isolated from the flower buds of Daphne genkwa which shows bioactivity against HeLa, HepG2, HT‐1080, MCF‐7, A549, U‐937, K562 and HL60 cell lines. It is the first time that a daphnane diterpenoid bearing a 1,10‐double bond was isolated. In this paper, B. Liu and co‐workers report asymmetric synthesis of the ring A substructure of genkwadane A in 10 steps from D‐tartrate derivative. More details are discussed in the article by Liu et al. on page 831–836.

     

Catalytic Asymmetric Synthesis of 2,2‐Disubstituted Oxetanes from Ketones by Using a One‐Pot Sequential Addition of Sulfur Ylide

Better the second time around : The title compounds were synthesized by using a one‐pot double methylene transfer catalyzed by a heterobimetallic La/Li complex. Chiral amplification in the second step was the key to obtaining oxetanes in high enantiomeric excess (see scheme).

     

Cover Picture: Recent Advances in Transition Metal‐Catalyzed Asymmetric Radical Reactions (Chin. J. Chem. 3/2018)

The control of stereoselectivity in radical reactions is of great importance, but remains a formidable challenge. The cover picture shows that the enantiomerically pure compounds can be prepared in radical transformations using chiral transition metal complexes as catalysts. Recent advances are summarized in the review by Kong et al. on page 247–256.

     

Back Cover: Electrochemical Radical Borylation of Aryl Iodides (Chin. J. Chem. 4/2019)

The back cover picture shows an electrochemical strategy for the borylation of aryl iodides via a radical pathway using current as a driving force. This method features mild reaction conditions, good functional groups tolerance, and prompt reaction time. EPR, CV and DPV experiments verified the formation of aryl radicals in this electrochemical borylation reaction, and the current plays an important role in the generation of radical intermediate. More details are discussed in the article by Mo et al. on page 347–351.

     

Inside Cover: Temperature‐responsive Catalyst for the Coupling Reaction of Carbon Dioxide and Propylene Oxide (Chin. J. Chem. 4/2018)

The inside cover picture shows a temperature controllable porphyrin aluminum catalyst using 5,10,15,20‐tetra(1,2,3,4,5,6,7,8‐octahydro‐1,4:5,8‐dimethanoanthracen‐9‐yl)porphyrin as ligand, which showed significantly temperature‐responsive selectivity in the coupling reaction of CO₂ and PO. Only cycloaddition reaction happened at temperature above 75 °C to produce 100% CPC, whereas copolymerization became dominant to afford PPC with selectivity over 91% at temperature below 50 °C. More details are discussed in the article by Wang et al. on page 299–305.

     

Inside Back Cover: Photochemical and Electrochemical Carbon Dioxide Utilization with Organic Compounds (Chin. J. Chem. 7/2018)

Inside Back Cover picture shows The carps trying hard to make a successful jump over the Dragon Gate will change into fish‐dragons, which is a legend handed down in China over generations. The back cover picture shows photochemical and electrochemical CO₂ transformations with organic compounds through the utilization of solar energy or electric energy, producing a series of valuable products, including carboxylic acids and hetero‐cyclic compounds. The combined utilization of both clean energy and CO₂ has attracted increasing attention in sustainable development of renewable energy and green chemistry. Recent advances are summarized by He et al. on page 644–659.

     

Combining Organocatalysis and Lanthanide Catalysis: A Sequential One‐Pot Quadruple Reaction Sequence/Hetero‐Diels–Alder Asymmetric Synthesis of Functionalized Tricycles

A stereoselective one‐pot synthesis of functionalized complex tricyclic polyethers has been achieved using the combination of secondary amine and lanthanide catalysis. This one‐pot quadruple reaction/Hetero‐Diels–Alder sequence gave good yields (per step) as well as excellent diastereo‐ and enantioselectivities. Furthermore, the particular combination of lanthanide complexes with organocatalysis is one of the first examples described for sequential catalysis.     

Inside Back Cover: Fabrication of Neutral Supramolecular Polymeric Films via Post‐electropolymerization of Discrete Metallacycles (Chin. J. Chem. 2/2018)

The inside back cover picture shows the construction of neutral supramolecular polymeric films containing well‐defined metallacycles as the main scaffolds through combination of coordination‐driven self‐assembly with post‐electropolymerization. A new 120° triphenylamine substituted dicarboxylate donor ligand and the complementary 120° triphenylamine functionalized di‐Pt(II) acceptor were employed to build neutral multi‐triphenylamine functionalized 2‐D metallacycles with the well‐defined shape and size via the formation of oxygen‐to‐platinum coordination bonds. Subsequent post‐electropolymerization of the obtained neutral multi‐triphenylamine containing metallacycles allowed for fabrication of a new type of neutral polymeric film with well‐controlled cavity sizes and thickness, which may have potential applications in neutral molecule detection, separation, and capture. More details are discussed in the article by Yang et al. on page 134–138.

     

Cover Picture: Highly Stable Molecular Borromean Rings (Chin. J. Chem. 2/2018)

The cover picture shows a series of Cp*Rh‐based molecular Borromean rings (BRs), which consist of three chemically independent rings that are locked in such a way that no two of the three rings are linked with each other. Interestingly, the structure of BRs is very similar to Kong Ming Lock (孔明锁), a kind of Chinese traditional six‐piece burr puzzle. In this work, some of as‐synthesized BRs display high stability in solution. The reason is related to the length ratio of the long‐arm linker and short‐arm linker, where smaller aspect ratios of the metallarectangles promote improved stability of the BRs in solution. Increasing the width of the metallaligand or pyridyl ligand hinders the formation of BRs and leads to unoccupied monomeric rectangles, which were further used as catalysts. More details are discussed in the article by Jin et al. on page 106–111.

     

Back Cover: Dual Stereocontrol for Enantioselective Hydrogenation of Dihydroisoquinolines Induced by Tuning the Amount of N‐Bromosuccinimide (Chin. J. Chem. 2/2018)

The back cover picture shows an efficient dual enantioselective synthesis of 1‐substituted 1,2,3,4‐tetrahydroisoquinoline, which was realized through iridium‐catalyzed hydrogenation of 1‐substituted 3,4‐dihydroisoquinolines. Only tuning the amount of N‐bromosuccinimide, this reaction promoted by (R)‐BINAP is able to furnish both enantiomers of products up to 89% ee (S) and 98% ee (R), respectively. Dual activation role of N‐bromosuccinimide is proposed to be responsible for the reversal of enantioselectivity under two hydrogenation conditions. More details are discussed in the article by Zhou et al. on page 139–142.