Scalable Total Synthesis of (+)-Desmethylxestospongin B.

Herein, the execution of synthetic strategies solving scalability issues observed in the original route is reported, increasing the total yield by 50% compared to the previously disclosed synthesis. A notable restructuring of the route's initial steps to reach a common allylic alcohol intermediate employs a highly stereoselective epoxidation method and avoids superfluous protecting group manipulations while limiting dependence on kinetic resolution in establishing stereochemistry for four of the six chiral centers in (+)-desmethylxestospongin B. Different protecting group strategies to avoid problems with their subsequent removal were considered and enacted; to this end, material was retained as byproducts were suppressed. While the lactam semireduction under Birch conditions requires further investigation, the updated synthesis of (+)-desmethylxestospongin B reported here made it more scalable, affording 0.37 g of this natural product for continued biological studies.

Concise Synthesis of (+)-[13 C4 ]-Anatoxin-a by Dynamic Kinetic Resolution of a Cyclic Iminium Ion.

An asymmetric total synthesis of [13 C4 ]-anatoxin-a ([13 C4 ]-1) has been developed from commercially available ethyl [13 C4 ]-acetoacetate ([13 C4 ]-15). The unique requirements associated with isotope incorporation inspired a new, robust, and highly scalable route, providing access to 0.110 g of this internal standard for use in the detection and precise quantification of anatoxin-a in freshwater. A highlight of the synthesis is a method that leverages a cyclic iminium ion racemization to achieve dynamic kinetic resolution in an enantioselective Morita-Baylis-Hillman (MBH) cyclization.

An Effective Bacterial Fucosidase for Glycoprotein Remodeling.

Fucose is an important component of many oligo- and polysaccharide structures as well as glycoproteins and glycolipids, which are often associated with a variety of physiological processes ranging from fertilization, embryogenesis, signal transduction, and disease progression, such as rheumatoid arthritis, inflammation, and cancer. The enzyme α-l-fucosidase is involved in the cleavage of the fucosidic bond in glycans and glycoconjugates, particularly the Fuc-α-1,2-Gal, Fuc-α-1,3/4-GlcNAc, and Fuc-α-1,6-GlcNAc linkages. Here, we report a highly efficient fucosidase, designated as BfFucH identified from a library of bacterial glycosidases expressed in E. coli from the CAZy database, which is capable of hydrolyzing the aforementioned fucosidic linkages, especially the α-1,6-linkage from the N-linked Fuc-α-1,6-GlcNAc residue on glycoproteins. Using BfFucH coupled with endoglycosidases and the emerging glycosynthases allows glycoengineering of IgG antibodies to provide homogeneous glycoforms with well-defined glycan structures and optimal effector functions.

Self-verification motives at the collective level of self-definition.

Three studies examined self-verification motives in relation to collective aspects of the self. Several moderators of collective self-verification were also examined--namely, the certainty with which collective self-views are held, the nature of one's ties to a source of self-verification, the salience of the collective self, and the importance of group identification. Evidence for collective self-verification emerged across all studies, particularly when collective self-views were held with high certainty (Studies 1 and 2), perceivers were somehow tied to the source of self-verification (Study 1), the collective self was salient (Study 2), and group identification was important (Study 3). To the authors' knowledge, these studies are the first to examine self-verification at the collective level of self-definition. The parallel and distinct ways in which self-verification processes may operate at different levels of self-definition are discussed.