Solvent-Induced Umpolung Reaction from Dioxygenation to C-S Coupling in Bis(2-phenylquinoline) Iridium(III) Thiolate Complexes.

The construction of C-S bonds is of great importance in the field of synthetic and medicinal chemistry. Herein, solvent-induced umpolung reactions from dioxygenation to interligand C-S cross-coupling in bis(cyclometalated) Ir(III) thiolate complexes are reported in good to excellent yields at room temperature. Specifically, the reaction of -[Ir(pq)(aet)] (where pq is 2-phenylquinoline and aet is 2-aminoethanethiolate) can be selectively switched to dioxygenation in acetonitrile solution in the presence of O, resulting in the formation of a sulfinato complex -[Ir(pq)(aes)] (where aes is 2-aminoethanesulfinato).

Switching the Photoreactions of Ir(III) Diamine Complexes between C-N Coupling and Dehydrogenation under Visible Light Irradiation.

The selective photoreactions under mild conditions play an important role in synthetic chemistry. Herein, efficient and mild protocols for switching the photoreactions of Ir(III)-diamine complexes between the interligand C-N coupling and dehydrogenation are developed in the presence of O in EtOH solution. The photoreactions of achiral diamine complexes -[Ir(L)(dm)](PF) (L is 2-phenylquinoline or 2-(2,4-difluorophenyl)quinoline, dm is 1,2-ethylenediamine, 1,2-diaminopropane, 2-methyl-1,2-diamino-propane, or ,-dimethyl-1,2-ethylenediamine) are competitive in the oxidative C-N coupling and dehydrogenation at room temperature, which can be switched into the interligand C-N coupling reaction at 60 °C, affording hexadentate complexes in good to excellent yields, or the dehydrogenative reaction in the presence of a catalytic amount of TEMPO as an additive, affording imine complexes.

Discrepancy between Proline and Homoproline in Chiral Recognition and Diastereomeric Photoreactivity with Iridium(III) Complexes.

The chiral-recognition processes of homoproline (hpro) and [Ir(pq)(MeCN)](PF) (pq is 2-phenylquinoline; MeCN is acetonitrile) are investigated, in favor of formation of the thermodynamically stable diastereomers Λ-[Ir(pq)(d-hpro)] and Δ-[Ir(pq)(l-hpro)]. Moreover, the diastereoselective photoreactions of Δ-[Ir(pq)(d-hpro)] and Δ-[Ir(pq)(l-hpro)] are reported in the presence of O at room temperature. Diastereomer Δ-[Ir(pq)(l-hpro)] is dehydrogenatively oxidized into imino acid complex Δ-[Ir(pq)(hpro-2H)] (hpro-2H is 3,4,5,6-tetrahydropicalinate), while diastereomer Δ-[Ir(pq)(d-hpro)] occurs by interligand C-N cross-coupling and dehydrogenative oxidation reactions, affording three products: Δ-[Ir(pq)(d-pqh)] [pqh is -(2-phenylquinolin-8-yl)homoproline], Δ-[Ir(pq)(hpro-2H)], and Δ-[Ir(pq)(d-hpro-2H)] [hpro-2H is 2,3,4,5-tetrahydropicalinate].

[Effect of electroacupuncture of acupoints on the healthy limb (opposing needling) on acute skeletal muscle contusion in rats].

Objective: To observe the therapeutic effect of electroacupuncture (EA) of "Zusanli" (ST36) and ""-point on the healthy side (opposing needling) on muscular injury and expression of myogenin (myoG) and fast myosin skeletal heavy chain (Fast MyHC) proteins in the gastrocnemius muscle (GM) tissues in skeletal muscle contusion rats，so as to explore its mechanism underlying improvement of skeletal muscle injury.

Methods: A total of 54 male SD rats were divided into normal control (n ＝ 6)，model (＝24) and opposing needling (EA, ＝24) groups. The latter two groups were further randomized into 3, 5, 7 and 14 d subgroups (＝6 per subgroup).