Preparation of polycyclic compounds by intramolecular photospirocyclization and photocycloaddition reactions of 4-alkenyl-1-cyanonaphthalene derivatives

Synthesis of 3‐Oxatricyclo[7.2.0.01,5]undeca‐7,10‐dienes through Intramolecular Photocycloaddition Reactions of Alkenes to 1,8 a‐Position of Naphthalene Ring

“…Reaction at the 1,2‐position that have high double bond character is the most common, and is described in many reports [13–70] . Reaction at the 1,3‐position via a biradical leads to compounds having a 3‐oxatricyclo[3.3.0.0 2,8 ]oct‐3‐ene skeleton, which was also shown in our earlier extensive studies [17,44,66,67,70–74] . The reaction at the 1,4‐position (photo‐Diels‐Alder reaction) proceeds stepwise mainly via excited triplet state [33,40,44,52,56,60,65,70,71,75–80] .…”

“…Reaction at the 1,3-position via a biradical leads to compounds having a 3oxatricyclo[3.3.0.0 2,8 ]oct-3-ene skeleton, which was also shown in our earlier extensive studies. [17,44,66,67,[70][71][72][73][74] The reaction at the 1,4-position (photo-Diels-Alder reaction) proceeds stepwise mainly via excited triplet state. [33,40,44,52,56,60,65,70,71,[75][76][77][78][79][80] In the reaction at the 1,8-position, tetrahydroacenaphthylene deriva-yields of 1,8a-adduct and secondary products is reported to be at most 30 % or less.…”

“…The reaction at the 1,4‐position (photo‐Diels‐Alder reaction) proceeds stepwise mainly via excited triplet state [33,40,44,52,56,60,65,70,71,75–80] . In the reaction at the 1,8‐position, tetrahydroacenaphthylene derivatives are obtained via the formation of zwitter ion and subsequent proton transfer [45,73,81–85] . Mixtures of compounds with different reaction modes are obtained in many photoreactions.…”

One and Two-Carbon Homologation of Primary and Secondary Alcohols to Corresponding Carboxylic Esters Using β-Carbonyl BT Sulfones as a Common Intermediate

“…However, when it comes to primary and secondary alcohols, in comparison only few options are available when the above-mentioned extensions are attempted. , The standard protocols used to extend an alcohol by one or two carbons requires in principle 3 distinct synthetic operations: (1) activation of the alcohol (transformation to a good-leaving group: GLG); (2) displacement of activated alcohol by C-nucleophile (e.g., cyanide for one carbon extension or carbonyl enolate for two carbon extension); and (3) transformation of the introduced functional group into the desired functionality (e.g., hydrolysis of nitrile to carboxylic acid; hydrolysis and monodecarboxylation of dimethylmalonate, etc. ).…”

Intramolecular Photocycloaddition Reactions of Arylcyclopropane Tethered 1-Cyanonaphthalenes

“…In contrast to their intermolecular counterparts, intramolecular reactions often take place with increased reaction rates, and high levels of regio- and stereoselectivity owing to close and pre-established locations of reactive centers. These phenomena have been considered in our recent design of linked alkene-naphthalene derivatives that undergo intramolecular photocycloaddition across the 1,3-position of the naphthalene ring and linked alkene-pyrene systems that undergo site-selective intramolecular photocycloaddition reactions . Up until now, no reports have appeared describing intramolecular photoreactions of arenes that contain tethered cyclopropane moieties.…”