Stereodivergent synthesis of benzylic alcohol derivatives enabled by Pd/Cu co-catalyzed asymmetric benzylic substitution reaction.

Despite their significant synthetic value, transition-metal-catalyzed asymmetric benzylic substitution reactions remain underexplored compared to the Tsuji-Trost reaction, primarily due to the inherent challenge associated with dearomatization. This reaction becomes much more challenging when constructing a stereogenic center at the benzyl position. Herein, we report a Pd/Cu co-catalyzed enantio- and diastereodivergent benzylic substitution reaction with benzyl geminal dicarboxylate, which is successfully applied for concurrent construction of two stereocenters at the benzyl position and nucleophile moiety.

Pd/Cu-Cocatalyzed Enantio- and Diastereodivergent Wacker-Type Dicarbofunctionalization of Unactivated Alkenes.

The Wacker and Wacker-type reactions are some of the most fundamental and powerful transformations in organic chemistry for their ability to efficiently produce valuable chemicals. Remarkable progress has been achieved in asymmetric oxy/aza-Wacker-type reactions; however, asymmetric Wacker-type dicarbofunctionalization remains underdeveloped, especially for the concurrent construction of two stereocenters. Herein, we report a Pd/Cu-cocatalyzed enantio- and diastereodivergent Wacker-type dicarbofunctionalization of alkene-tethered aryl triflates with imino esters.

Nickel/Copper-Cocatalyzed Asymmetric Benzylation of Aldimine Esters for the Enantioselective Synthesis of α-Quaternary Amino Acids.

The first asymmetric Ni/Cu cocatalyzed benzylation of aldimine esters is reported. A series of benzyl-substituted α-quaternary amino acids could be synthesized in high yield and with high levels of enantioselectivity (up to 90 % yield and 99 % ee). The experimental and theoretical calculation results suggested that the strong electrophilicity of the η -benzylnickel intermediate is crucial for the high reactivity, enabling the reaction under base-free conditions.

Bickerstaff's brainstem encephalitis, Miller Fisher syndrome and Guillain-Barré syndrome overlap in an asthma patient with negative anti-ganglioside antibodies.

Background: Bickerstaff's brainstem encephalitis (BBE), together with Miller Fisher syndrome (MFS) and Guillain-Barré syndrome (GBS) were considered to form a continuous clinical spectrum. An anti-GQ1b antibody syndrome has been proposed to underlie the common pathophysiology for the three disorders; however, other studies have found a positive anti-GM1 instead of anti-GQ1b antibody.

Case Presentation: Here we report a 20-year-old male patient with overlapping BBE, MFS and GBS.