Synthesis of Axially Chiral Styrenes through Pd-Catalyzed Asymmetric C−H Olefination Enabled by an Amino Amide Transient Directing Group

The atroposelective synthesis of axially chiral styrenes remains a formidable challenge due to their relatively lower rotational barriers compared to the biaryl atropoisomers. Herein, we describe the construction of axially chiral styrenes through Pd^II-catalyzed atroposelective C−H olefination, using a bulky amino amide as a transient chiral auxiliary. Various axially chiral styrenes were produced with good yields and high enantioselectivity (up to 95 % yield and 99 % ee). Carboxylic acid derivatives of the resulting axially chiral styrenes showed superior enantiocontrol over the biaryl counterparts in Co^III-catalyzed enantioselective C(sp³)−H amidation of thioamide. Mechanistic studies suggest that C−H cleavage is the enantioselectivity-determining step.     

Palladium/graphitic carbon nitride catalyst for selective oxygen transfer in Wacker oxidation

Nanoscaled palladium particles supported on graphitic carbon nitride (Pd⁰/g-C₃N₄) is prepared to improve the oxygen transfer in Wacker oxidation via chemical reduction method. From the analysis of FT-IR, XRD, SEM, TEM, XPS and ICP, Pd⁰ particles are firmly combined with g-C₃N₄ layers, and sub-surface ones occupy most of the components. It is worth mentioning that graphene oxide (GO), which is completely recyclable without further pollution, can be used as a ‘solid weak acid’ taking the place of H₂SO₄ and CF₃COOH. Under the optimization conditions, as many as 46 kinds of olefins are transferred into corresponding products with satisfactory yields, and o-methyl styrene gets the highest yield of 94%. After five times of recycling experiment, the yield of acetophenone only decreases by about 7.0% in the uniform reaction process. In virtue of former research results and molecular electrostatic potential, a possible mechanism is put forward to explain the catalytic process.     

Enantioselective Synthesis of Isoxazolines Enabled by Palladium-Catalyzed Carboetherification of Alkenyl Oximes

Reported here is a highly efficient Pd/Xiang-Phos catalyzed enantioselective carboetherification of alkenyl oximes with either aryl or alkenyl halides, delivering various chiral 3,5-disubstituted and 3,5,5-trisubstituted isoxazolines in good yields with up to 97 % ee. The sterically bulky and electron-rich (S,Rs)- NMe-X2 ligand is responsible for the excellent reactivities and enantioselectivities. The salient features of this transformation include mild reaction conditions, general substrate scope, good functional-group tolerance, good yields, high enantioselectivities, easy scale-up, and application in the late-stage modification of bioactive compounds. The obtained products can be readily transformed into useful chiral 1,3-aminoalcohols.     

Synergistic N-Heterocyclic Carbene/Palladium-Catalyzed Umpolung 1,4-Addition of Aryl Iodides to Enals

An umpolung 1,4-addition of aryl iodides to enals promoted by cooperative (terpy)Pd/NHC catalysis was developed that generates various bioactive β,β-diaryl propanoate derivatives. This system is not only the first reported palladium-catalyzed arylation of NHC-bound homoenolates but also expands the scope of NHC-induced umpolung transformations. A diverse array of functional groups such as esters, nitriles, alcohols, and heterocycles are tolerated under the mild conditions. This method also circumvents the use of moisture-sensitive organometallic reagents.     

Enantioselective Difunctionalization of Alkenes by a Palladium-Catalyzed Heck/Sonogashira Sequence

Sonogashira-type cross-couplings are one of the most significant alkynylations in organic chemistry. One of the first palladium-catalyzed intramolecular Heck/Sonogashira reactions of alkenes with terminal alkynes is now reported. With this method, a variety of uniquely substituted chiral benzene-fused heterocycles bearing a propargyl-substituted all-carbon quaternary stereocenter were obtained in a straightforward, high-yielding, and highly stereoselective manner under mild conditions. Salient features of this process include the use of readily available substrates, high selectivities, a broad substrate scope as well as versatile product functionalizations.