Synlett

An attempted aryl selenium-catalyzed formation of cis-chlorohydrins from alkenes was unsuccessful but led to an electrochemical investigation for the trans-selective chloroformyloxylation of cyclic and acyclic alkenes in moderate to good yields. Interestingly, when 1,1-disubstituted alkenes were used, the corresponding vinyl chloride derivatives were obtained, and the application of 1-phenylcyclohex-1-ene led to the formation of an allyl chloride derivative.

Synlett 2024; 35: XV-XVIDOI: 10.1055/s-0043-1763724Georg Thieme Verlag KG Rüdigerstraße 14, 70469 Stuttgart, GermanyArticle in Thieme eJournals:Table of contents

Over the past two decades, bioorthogonal chemistry has profoundly impacted various chemistry-related fields, including chemical biology and drug delivery. This transformative progress stems from collaborative efforts involving chemists and biologists, underscoring the importance of interdisciplinary research. In this Account, we present the developments in bioorthogonal chemistry within our Institute for Molecules and Materials at Radboud University. The chemistry disclosed here spans from strained alkynes and alkenes to drug release and bioconjugation strategies, mirroring the extensive scope provided by bioorthogonal chemistry. By reflecting on the chemistry originating at Radboud University, this Account emphasizes that teamwork is essential for driving significant progress in bioorthogonal chemistry.1 Introduction2 Providing BCN as a Robust Bioorthogonal Tool for Chemical Biology and Beyond3 Towards Readily Available Click-to-Release trans-Cyclooctenes4 Giving Molecules Guidance5 Next Generation of Bioconjugation Strategies: Dynamic Click Chemistry6 Conclusions

The nickel-catalyzed borylative coupling of aldehydes and 1,3-dienes with diboron reagents offers an efficient method for synthesizing valuable homoallylic alcohols from easily accessible starting materials. However, achieving enantioselectivity in this reaction has been a significant challenge. We discuss our recent report on the first example of a nickel-catalyzed enantioselective borylative coupling of aldehydes with 1,3-dienes, employing a chiral spiro-phosphine–oxazoline ligand. Notably, by utilizing (E)-1,3-dienes or (Z)-1,3-dienes, we can reverse the diastereoselectivity, yielding either anti- or syn-products, respectively.

Synlett 2024; 35: A53-A69DOI: 10.1055/s-0040-1720628Georg Thieme Verlag KG Rüdigerstraße 14, 70469 Stuttgart, GermanyArticle in Thieme eJournals:Table of contents

Synlett 2024; 35: V-DOI: 10.1055/s-0043-1763694Georg Thieme Verlag KG Rüdigerstraße 14, 70469 Stuttgart, GermanyArticle in Thieme eJournals:Table of contents

Synlett 2024; 35: 734-734DOI: 10.1055/s-0043-1763692Georg Thieme Verlag KG Rüdigerstraße 14, 70469 Stuttgart, GermanyArticle in Thieme eJournals:Table of contents  |  Full text

Photoinduced carbamoylation of ethers using isocyanates as amide sources was accomplished under mild and environmentally friendly reaction conditions. A series of isocyanates were tolerated in this protocol to construct α-amide-substituted ether derivatives with desired yields. The method featured broad substrate scope and good functional group tolerance, which could play an important role in the construction of biological molecules with ethers.

A simple approach for the synthesis of the alkaloid racemosin B has been developed through a photochemical cyclization reaction with a 33% overall yield without any reagents. This method is sustainable and environmentally friendly because no reagents are required to effect the transformation.

We have established an innovative protective approach that disrupts intermolecular interactions to enhance substrate reactivity. Specifically, diacetylimide protection of acetamide prevents the formation of hydrogen bonds, while the incorporation of tert-butyl groups on the aromatic protecting group disrupts π-stacking interactions, both of which culminate in heightened reactivity in glycosylations. We explored the synergistic implementation of these protective measures and applied them to the synthesis of 6-sulfo sialyl Lewis X.