Work

Flow Photochemical Syntheses of trans‐Cyclooctenes and trans‐Cycloheptenes Driven by Metal Complexation

Year: 2019

Type: article

Abstract: trans‐Cyclooctenes and trans‐cycloheptenes have long been the subject of physical organic study, but the broader application had been limited by synthetic accessibility. This account describes the development of a general, flow photochemical method for the preparative synthesis of trans‐cycloalkene derivatives. Here, photoisomerization takes place in a closed‐loop flow reactor where the reaction mixture is continuously cycled through Ag(I) on silicagel. Selective complexation of the trans‐isomer by Ag(I) during flow drives an otherwise unfavorable isomeric ratio toward the trans‐isomer. Analogous photoreactions under batch‐conditions are low yielding, and flow chemistry is necessary in order to obtain trans‐cycloalkenes in preparatively useful yields. The applications of the method to bioorthogonal chemistry and stereospecific transannulation chemistry are described.

Source: Israel Journal of Chemistry

DOI: 10.1002/ijch.201900085

Authors: Jessica E. Pigga, Joseph M. Fox

Institution: University of Delaware

Language: English

Topic: Innovative Microfluidic and Catalytic Techniques Innovation

Subfield: Biomedical Engineering

Field: Engineering

Domain: Physical Sciences

Open Access status: green

Funders: National Institutes of Health, National Institute of General Medical Sciences

Awards: Discovery of Chemical Probes and Therapeutic Leads, Phase II, Toolkit for Fast, Multipurpose and Inducible Bioorthogonal Chemistry