Integrating Regioselective E→Z Isomerization of Trienones with Cascade Sequences under Photosensitizer‐Free Direct Irradiation at 390 nm

Abstract

AbstractThe regioselective E→Z isomerization of a target olefin unit embedded in a conjugated polyene is challenging. Examples are limited to retinal and its derivatives only. The problem is further amplified when such an isomerization is integrated into cascade sequences, among which the regioselectivity and subsequent directionality are the major bottlenecks. Indeed, there are no reports till date for such a transformation. Herein, it is reported that such a controlled isomerization and subsequent cyclization cascade can be enabled by photosensitizer‐free direct irradiation of linearly conjugated acyclic polyenes in dichloromethane solvent using a 390 nm LED. The directionality results from deconjugation of the extended π‐system in the transient Z‐isomer due to stabilizing n→π* interactions between 1,4‐dicarbonyls (C=O→C=O) or 1,4‐carbonyl/‐aryl (C=O→aryl) groups. The involvement of such noncovalent interactions has been supported by X‐ray crystallography and control experiments. Thus, conjugated trienones can be stereoselectively converted into oxabicyclo[3.2.1]octadienes in an atom‐ and step‐economic manner, including the first example by regioselective isomerization of a tetrasubstituted alkene. The reaction conditions are very general (>46 examples). The reaction can be conducted under open air atmosphere at ambient temperature. Such a cascade cyclization can also be realized in solid state.