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Cucurbiturils as Reaction Containers for Photocycloaddition of Olefins
Author(s) -
Pattabiraman Mahesh,
Sivaguru Jayaraman,
Ramamurthy V.
Publication year - 2018
Publication title -
israel journal of chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.908
H-Index - 54
eISSN - 1869-5868
pISSN - 0021-2148
DOI - 10.1002/ijch.201700100
Subject(s) - chemistry , photoisomerization , cyclobutanes , alkene , cucurbituril , dimer , cycloaddition , molecule , photochemistry , combinatorial chemistry , computational chemistry , organic chemistry , isomerization , supramolecular chemistry , catalysis
The [2+2] photocycloaddition (PCA [2+2]) of alkenes is one of the most synthetically useful photoreactions. It is a convenient one‐step reaction that is useful for generating substituted cyclobutanes, polymers, and biologically relevant molecules. However, the reaction efficiency is limited by its bimolecular nature requiring encounter between two reactants within the narrow window of excited state lifetime of the photoactive alkene, and competition from the unimolecular photoisomerization. Our groups have utilized macrocyclic cavitands, especially cucurbiturils(CB), to confine two alkene molecules within their cavities and steer them towards a single dimer regio‐ and stereoselectively. Although, primarily the review focuses on photocycloaddition within CBs, such reactions in closely related cavitands such as cyclodextrins (CD) and calixarenes (CA) are also briefly mentioned to provide a comparison with CBs. Studies on photocycloaddition of olefins within CB by other research groups are also briefly highlighted. A mechanistic model, with ability to predict the nature of the dimer product formed within the above reaction containers is included.