We report a novel and highly stereoselective electro‐2‐deoxyglycosylation from glycals. This method features excellent stereoselectivity, scope, and functional‐group tolerance. This process can also be applied to the modification of a wide range of natural products and drugs. Furthermore, a scalable synthesis of glycosylated podophyllotoxin and a one‐pot trisaccharide synthesis through iterative electroglycosylations were achieved.

A visible‐light‐promoted iterative synthesis of 2‐deoxyoligosaccharides is reported by De‐Cai Xiong, Xin‐Shan Ye, and co‐workers in their Research Article (e202114726). The rapid constructions of oligosaccharides, 20‐mer deoxyglycan, and digoxin are facilitated by a bromide‐based hydrogen species through an electron transfer process.

A one-pot three-enzyme protocol was developed by engineering a bacterial sialyltransferase to facilitate the modification of therapeutic antibodies with N-acetylneuraminic acid or its derivatives towards optimized glycosylation.

The photoinitiated intramolecular hydroetherification of alkenols has been used to form C−O bonds, but the intermolecular hydroetherification of alkenes with alcohols remains an unsolved challenge. We herein report the visible‐light‐promoted 2‐deoxyglycosylation of alcohols with glycals. The glycosylation reaction was completed within 2 min in a high quantum yield (ϕ=28.6). This method was suitable for a wide array of substrates and displayed good reaction yields and excellent stereoselectivity. The value of this protocol was further demonstrated by the iterative synthesis of 2‐deoxyglycans with α‐2‐deoxyglycosidic linkages up to a 20‐mer in length and digoxin with β‐2‐deoxyglycosidic linkages. Mechanistic studies indicated that this reaction involved a glycosyl radical cation intermediate and a photoinitiated chain process.

Fused-silica glass, as a desirable material with rigidity, biological inertness, and favorable light transmission for nanofluidic devices, should be assembled via low-temperature bonding technology to hermetically seal channels for stable...