Ir‐Catalyzed Asymmetric Hydrogenation of α‐Alkylidene β‐Lactams and Cyclobutanones

Chiral β‐lactams and cyclobutanones are present in numerous natural and pharmaceutical products. The stereoselective construction of chiral four‐membered cyclic compounds is an ongoing challenge for the chemical community. Herein, we report a highly stereocontrolled construction of four‐membered ring (mini‐sized) β‐lactams and cyclobutanones via an Ir/ In‐BiphPHOX ‐catalyzed asymmetric hydrogenation, providing the corresponding optically active four‐membered ring carbonyl products bearing an α‐chiral carbon center with excellent yields (up to 99%) and enantioselectivities (up to 98%) under mild reaction conditions (1.0—2.5 bar H₂ for 1.0—10 h). The reaction presents wide substrate scope. Diverse transformations of the catalyzed products were also conducted to show the potential utility of this protocol.     

Inside Cover: Palladium‐Catalyzed Asymmetric Dihydroxylation of 1,3‐Dienes with Catechols (Chin. J. Chem. 3/2019)

The inside cover picture shows a palladium‐catalyzed asymmetric dihydroxylation of 1,3‐dienes with catechols utilizing chiral pyridinebis(oxazoline) ligand. The reaction is proposed to proceed via a cascade Wacker‐type hydroxypalladation/asymmetric allylation process. This methodology provides a direct and straightforward synthesis to prepare chiral 2‐substituted 1,4‐benzodioxane motifs in moderate to good yield and enantioselectivity from readily available starting materials. More details are discussed in the article by Gong et al. on page 226–232.

     

SpinPhox/Iridium(I)‐Catalyzed Asymmetric Hydrogenation of Cyclic α‐Alkylidene Carbonyl Compounds

Optically active medium‐sized cyclic carbonyl compounds bearing an α‐chiral carbon center are of interest in pharmaceutical sciences and asymmetric synthesis. Herein, SpinPhox/Ir^I catalysts have been demonstrated to be highly enantioselective in the asymmetric hydrogenation of the CC bonds in the exocyclic α,β‐unsaturated cyclic carbonyls, including a broad range of α‐alkylidene lactams, unsaturated cyclic ketones, and lactones. It is noteworthy that the procedure can be successfully used in the asymmetric hydrogenation of the challenging α‐alkylidenelactam substrates with six‐ or seven‐membered rings, thus affording the corresponding optically active carbonyl compounds with an α‐chiral carbon center in generally excellent enantiomeric excesses (up to 98 % ee). Synthetic utility of the protocol has also been demonstrated in the asymmetric synthesis of the anti‐inflammatory drug loxoprofen and its analogue, as well as biologically important ε‐aminocaproic acid derivatives.     

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.

     

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.

     

Cover Picture: Palladium‐Catalyzed Intermolecular Oxidative Coupling Reactions of (Z)‐Enamines with Isocyanides through Selective β‐C(sp2)‐H and/or C=C Bond Cleavage (Chin. J. Chem. 8/2018)

The cover picture shows Two efficient intermolecular oxidative coupling reactions of (Z)‐enamines with isocyanides via palladium catalysis have been developed. In these transformations, the β‐C(sp²)‐H and/or C ＝ C bond were cut off selectively by using different anionic ligands, leading to controllable chemodivergent and stereoselective construction of a wide range of (E)β‐carbamoylenamine derivatives with intramolecular hydrogen bonds. More details are discussed in the article by Jiang et al. on page 712–715.

     

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.

     

Cover Picture: Understanding Zeolites Catalyzed Methanol‐to‐Olefins Conversion from Theoretical Calculations (Chin. J. Chem. 5/2018)

The cover picture shows the complexity of the reaction mechanism of zeolites catalyzed methanol‐to‐olefins (MTO) conversion. The MTO process plays a vital role in the production of light olefins from nonpetroleum resources. Despite of the successful industrialization of the MTO process in China, the detailed reaction mechanism is not yet well understood. The theoretical studies on the MTO hydrocarbon pool mechanism by the Group of Xie are summarized in the Chemistry Author Up Close by Xie et al. on page 381–386.

     

Ir‐SpinPHOX Catalyzed Enantioselective Hydrogenation of 3‐Ylidenephthalides

The first asymmetric hydrogenation of 3‐ylidenephthalides has been developed using the Ir^I complex of a spiro[4,4]‐1,6‐nonadiene‐based phosphine‐oxazoline ligand (SpinPHOX) as the catalyst, affording a wide variety of chiral 3‐substituted phthalides in excellent enantiomeric excesses (up to 98 % ee). The utility of the protocol has been demonstrated in the asymmetric synthesis of chiral drugs NBP and BZP precursor, as well as the natural products chuangxinol and typhaphthalide.