Asymmetric Synthesis of Hydroindoles via Desymmetrizing [3+2] Annulation of p-Quinamines and Arylalkylketenes.

The asymmetric desymmetrizing [3+2] annulation reaction of p-quinamines and arylalkylketenes to synthesize hydroindoles was realized. Catalyzed by chiral bisguanidinium hemisalt via multiple hydrogen bond interactions, enantiomerically enriched products with reversal of diastereoselectivity in comparison with the racemic version were afforded in good yields under mild reaction conditions. Diaryl-substituted hydroindoles could also perform the Friedel-Crafts type of addition to give more complicated multicycles. Density functional theory calculations revealed that the enantio- and diastereoselectivity stem from varied hydrogen-bonding manners.

Sterically Hindered and Deconjugative α-Regioselective Asymmetric Mannich Reaction of Meinwald Rearrangement-Intermediate.

Compared to γ-addition, the α-addition of α-branched ß,γ-unsaturated aldehydes faces larger steric hindrance and disrupts the π-π conjugation, which might be why very few examples are reported. In this article, a highly diastereo- and enantioselective α-regioselective Mannich reaction of isatin-derived ketimines with α-, ß- or γ-branched ß,γ-unsaturated aldehydes, generated in situ from Meinwald rearrangement of vinyl epoxides, is realized by using chiral N,N'-dioxide/ScIII catalysts. A series of chiral α-quaternary allyl aldehydes and homoallylic alcohols with vicinal multisubstituted stereocenters are constructed in excellent yields, good d.r. and excellent ee values. Experimental studies and DFT (density functional theory) calculations reveal that the large steric hindrance of the ligand and the Boc (tButyloxy carbonyl) protecting group of imines are critical factors for the α-regioselectivity.

Enantioselective Formal Vinylogous N-H Insertion of Secondary Aliphatic Amines Catalyzed by a High-Spin Cobalt(II) Complex.

Vinylcarbene insertion into the nitrogen-hydrogen (N-H) bond of amines allows direct access to α,ß-unsaturated γ-amino acid derivatives, meeting a marked challenge in the control of regio- and enantioselectivities. Here, we report a highly γ-selective and enantioselective insertion into N-H bonds of aliphatic or aromatic secondary amines with vinyl substituted α-diazo pyrazoleamides using a high-spin chiral N,N'-dioxide/cobalt(II) complex catalyst. The method affords a wide variety of valuable optically active Z- and E-type vinyl γ-amino amides. Calculation reveals a spin state change from the quartet cobalt(II) complex to a doublet Co(II)-carbene species for facile Z-selective and enantioselective nucleophilic addition.

Asymmetric Catalytic Vinylogous Addition Reactions Initiated by Meinwald Rearrangement of Vinyl Epoxides.

The first catalytic asymmetric multiple vinylogous addition reactions initiated by Meinwald rearrangement of vinyl epoxides were realized by employing chiral N,N'-dioxide/ScIII complex catalysts. The vinyl epoxides, as masked ß,γ-unsaturated aldehydes, via direct vinylogous additions with isatins, 2-alkenoylpyridines or methyleneindolinones, provided a facile and efficient way for the synthesis of chiral 3-hydroxy-3-substituted oxindoles, α,ß-unsaturated aldehydes and spiro-cyclohexene indolinones, respectively with high efficiency and stereoselectivity. The control experiments and kinetic studies revealed that the Lewis acid acted as dual-tasking catalyst, controlling the initial rearrangement to match subsequent enantioselective vinylogous addition reactions. A catalytic cycle with a possible transition model was proposed to illustrate the reaction mechanism.

NiFe Oxalate Nanomesh Array with Homogenous Doping of Fe for Electrocatalytic Water Oxidation.

NiFe-based materials have shown impressive electrocatalytic activity for the oxygen evolution reaction (OER). The mutual effect between proximate Ni and Fe atoms is essential in regulating the electronic structure of the active site to boost the OER kinetics. Detailed studies confirm that the separated monometal phases in NiFe-based materials are detrimental to OER. Thus, the high-level blending of Ni and Fe in NiFe-based OER electrocatalysts is critical. Herein, an NiFe oxalate nanomesh array based on solid solutions between nickel (II) oxalate and iron (II) oxalate is prepared through a facile surfactant-free approach in the presence of the reductive oxalate anions. The integrated electrode can efficiently catalyze water oxidation to reach a current density of 50 mA cm-2 with a small overpotential of 203 mV in a 1.0 m KOH aqueous solution. The high efficiency can be attributed to the atomic level mix of Ni and Fe in the solid solutions and the hierarchical porous structure of the nanomesh array. These two aspects bring about fast kinetics, efficient mass diffusion, and quick charge transfer, which are the three major positive factors for a high-performance heterogenous electrocatalyst.