Cycloisomerization of Olefins in Water. (28th May 2020)

• Record Type: Journal Article
• Authors: Matos, Jeishla L. M.; Green, Samantha A.; Chun, Yuge; Dang, Vuong Q.; Dushin, Russell G.; Richardson, Paul; Chen, Jason S.; Piotrowski, David W.; Paegel, Brian M.; Shenvi, Ryan A.
• Is Part Of: Angewandte Chemie. Volume 132:Number 31(2020)
• Page Start: 13098
• Page End: 13103
• Publication Date: 2020-05-28
• Subjects: DNA -- cobalt -- isomerization -- kinetics -- water chemistry; Chemistry -- Periodicals; 540
• DOI: 10.1002/ange.202003948
• Languages: English
• ISSNs: 0044-8249

Abstract

Abstract: Preparative reactions that occur efficiently under dilute, buffered, aqueous conditions in the presence of biomolecules find application in ligation, peptide synthesis, and polynucleotide synthesis and sequencing. However, the identification of functional groups or reagents that are mutually reactive with one another, but unreactive with biopolymers and water, is challenging. Shown here are cobalt catalysts that react with alkenes under dilute, aqueous, buffered conditions and promote efficient cycloisomerization and formal Friedel–Crafts reactions. The constraining conditions of bioorthogonal chemistry are beneficial for reaction efficiency as superior conversion at low catalyst concentration is obtained and competent rates in dilute conditions are maintained. Efficiency at high dilution in the presence of buffer and nucleobases suggests that these reaction conditions may find broad application. Abstract : Virtues we write in water : Cobalt‐catalyzed cycloisomerization occurs with efficiency in aqueous buffer at high dilution. A variety of putative metal hydride atom‐transfer (MHAT) reactions, including deallylation, proceed under these stringent conditions, even on DNA.