Enediyne Photocyclizations Tool for Cancer Therapy

Selective photochemical initiation is a viable option for inducing cycloaromatizations of enediynes and related compounds. Although increasing the efficiency of photochemical cycloaromatizations has been shown to be feasible, further research is needed to fully elucidate the electronic factors that control these processes. The presence of two orthogonal x-systems in alkynes is important for the understanding and control of photochemical cycloaromatization reactions since the two x-systems play complementary and important roles. 

Francisco Galindo M. Consuelo Jimenez, and Miguel Angel Miranda  

More than half a century ago, Anderson and Reese reported the first example of a photo-Fries rearrangement (PFR), where 2-hydroxyphenylacetate was converted into 2,3- and 3,4-dihydroxy acetophenone upon UV irradiation [1]. Since then, hundreds of articles have appeared on this reaction, which has been extended from the initial aryl esters to amides, carbonates, carbamates, thioesters, sulfonates, etc. [2-4]. 

The present chapter covers the publications on PFR appearing until the end of 2013, with special emphasis on the developments of the last decade. In addition to recent synthetic applications, the accumulated mechanistic evidence based on direct spectroscopic studies and the peculiarities of the reaction in organized and constrained media are highlighted. 

---