[2.2]Benzoindenophane-Based Chiral Indenyl Ligands: Design, Synthesis, and Applications in Asymmetric C-H Activation.

Development of chiral indenyl ligands for asymmetric C-H activation is a longstanding challenge, and extremely few successes have been achieved. In this paper, we describe a class of readily accessible, facilely tunable and user-friendly chiral indenyl ligands featuring a [2.2]benzoindenophane skeleton via a divergent synthesis strategy. The corresponding chiral indenyl rhodium catalysts were successfully applied in the asymmetric C-H activation reaction of O-Boc hydroxybenzamide with alkenes to give various chiral dihydroisoquinolone products (up to 97 % yield, up to 98 % ee). Moreover, the asymmetric C-H activation reaction of carboxylic acids with alkynes was also successfully accomplished, providing a range of axially chiral isocoumarins (up to 99 % yield, up to 94 % ee). Notably, this represents the first example of enantioselective transition metal catalyzed C(sp2)-H activation/oxidative coupling of benzoic acids with internal alkynes to construct isocoumarins. Given many attractive features of this class of indenyl ligands, such as convenient synthesis, high tunability and exclusive face-selectivity of coordination, its applications in more catalytic asymmetric C-H activation and in other asymmetric catalysis are foreseen.

H8-BINOL-Derived Chiral η6-Benzene Ligands: New Opportunities for the Ruthenium-Catalyzed Asymmetric C-H Activation.

Given the tremendous success of (p-cymene)RuII-catalyzed C-H activation over the past 20 years, the community has long been aware that the development of chiral η6-benzene (Ben) ligands should be a potent strategy for achieving the attractive but incredibly underdeveloped ruthenium(II)-catalyzed asymmetric C-H activation. However, it has rarely been achieved due to the severe difficulty in developing proper chiral Ben ligands. In particular, designing chiral Ben ligands by connecting a benzene fragment to a chiral framework including benzene rings remained an unsolved challenge until this effort. Here we present a novel class of axially chiral Ben ligands derived from readily available (S)-5,5',6,6',7,7',8,8'-octahydro-1,1'-bi-2-naphthol ((S)-H8-BINOL) in 4-8 steps. Notably, when coordinated with ruthenium, such chiral Ben ligand containing three benzene rings only forms one of the three possible isomeric BenRuII complexes. The related chiral BenRuII catalysts could effectively catalyze the asymmetric C-H activation of N-sulfonyl ketimines with alkynes, affording a range of chiral spirocyclic sultams in up to 99 % yield with up to >99 % ee. These catalysts are expected to find broad applications in future.

Chiral 3,3,3',3'-Tetramethyl-1,1'-Spirobiindanyl Cyclopentadienyl (TMSCp) Ligands: Design, Synthesis, and Applications.

Chiral cyclopentadienyl (Cp) rhodium(III) are powerful catalysts for achieving asymmetric C-H activation. This paper describes the design and synthesis of a new type of chiral Cp ligand bearing a chiral 3,3,3',3'-tetramethyl-1,1'-spirobiindanyl backbone. It features convenient synthesis, easy modification, and relatively low cost. Moreover, it holds great potential in achieving asymmetric C-H activation as exemplified by four examples examined in this work.

Chiral Arene Ligand as Stereocontroller for Asymmetric C-H Activation.

Development of chiral ligands is the most fundamental task in metal-catalyzed asymmetric synthesis. In the last 60 years, various kinds of ligands have been sophisticatedly developed. However, it remains a long-standing challenge to develop practically useful chiral η6 -arene ligands, thereby seriously hampering the asymmetric synthesis promoted by arene-metal catalysts. Herein, we report the design and synthesis of a class of readily tunable, C2 -symmetric chiral arene ligands derived from [2.2]paracyclophane. Its ruthenium(II) complexes have been prepared and successfully applied in the enantioselective C-H activation to afford a series of axially chiral isoquinolones (up to 99 % yield and 96 % ee). This study not only lays chemists' longstanding doubts about whether it is possible to use chiral arene ligands to stereocontrol ruthenium(II)-catalyzed asymmetric C-H activation, but also opens up a new avenue to achieve asymmetric C-H activation.

Synthesis of Uranium Single Atom from Radioactive Wastewater for Enhanced Water Dissociation and Hydrogen Evolution.

As a common nuclide in radioactive wastewater, uranium (U) is generally treated by landfill, which induces the massive abandonment of uranium resources. In this work, a pulse voltammetry method for the synthesis of U single atoms on MoS2 (U/MoS2 ) nanosheets from radioactive wastewater for the electrocatalytic alkaline hydrogen evolution reaction (HER) is reported. The mass loading of U single atoms is facilely controlled with high selectivity for coexisting ions in radioactive wastewater. In the electrolyte of 1 m of KOH, U/MoS2 nanosheets with 5.2% of U single atoms exhibit relatively low overpotentials of 72 mV at 10 mA cm-2 . The mechanistic study reveals that the HER on U/MoS2 includes the water dissociation on U single atoms to form OH* and H transfer from OH* to adjacent S-edge atoms. This procedure exhibits decreased activation energy for transition state in water dissociation and optimized Gibbs free energy for H* adsorption.

Development of a C2-Symmetric Chiral aza Spirocyclic Diol.

A C2-symmetric chiral spirocyclic diol aza-SPINOL containing a spirooxindole scaffold has been designed, synthesized, and optically resolved. The product could be synthesized on gram scale in an overall yield of 22%. Moreover, elaborations of aza-SPINOL to other chiral ligands as well as the preliminary investigation of the related bisphosphine ligand in the desymmetrization of bisallylic amide were reported.

Ruthenium(II)-Catalyzed Asymmetric Inert C-H Bond Activation Assisted by a Chiral Transient Directing Group.

A ruthenium(II)-catalyzed asymmetric intramolecular hydroarylation assisted by a chiral transient directing group has been developed. A series of 2,3-dihydrobenzofurans bearing chiral all-carbon quaternary stereocenters have been prepared in remarkably high yields (up to 98 %) and enantioselectivities (up to >99 % ee). By this methodology, a novel asymmetric total synthesis of CB2 receptor agonist MDA7 has been successfully developed.

N-Methoxyamide: An Alternative Amidation Reagent in the Rhodium(III)-Catalyzed C-H Activation.

In the field of transition-metal-catalyzed C-H activation, N-methoxyamides are widely used as C-H activation substrate. Unexpectedly, in this work N-methoxyamides were found to work as efficient amidation reagents in the rhodium(III)-catalyzed C-H activation with boric acid as a cocatalyst. This reaction features broad substrate scope and good yields.

Enantioselective Synthesis of C-N Axially Chiral N-Aryloxindoles by Asymmetric Rhodium-Catalyzed Dual C-H Activation.

The first enantioselective Satoh-Miura-type reaction is reported. A variety of C-N axially chiral N-aryloxindoles have been enantioselectively synthesized by an asymmetric rhodium-catalyzed dual C-H activation reaction of N-aryloxindoles and alkynes. High yields and enantioselectivities were obtained (up to 99 % yield and up to 99 % ee). To date, it is also the first example of the asymmetric synthesis of C-N axially chiral compounds by such a C-H activation strategy.