Benzylic C-H bonds functionalization

Jang and co-workers explored the asymmetric a-alkylation of aldehydes with xanthene by merging electro-oxidation and organocatalysis to synthesize the corresponding xanthene-derived benzylic products 65a in up to 68% yield and 68% ee (Scheme 2.22). This study showed that anodic oxidation, in addition to stoichiometric amounts of chemical oxidation, was applicable to the benzylic C—H bond functionalization for coupling with enamine. 

Selective cleavage and functionalization of allylic C(sp )-H bonds is a synthetically attractive strategy (Scheme 2.20). The pioneering work has illustrated the possibility of allylic C-H bond using electrophilic i-allylpalladium intermediates. In recent years, the transition-metal-catalyzed selective allylic and benzylic C-H bond functionalization gained particular interests. 

In this chapter, we have used computational tools to study the (PDI)Ca-catalyzed benzylic C-H bond functionalization by diazocarbenes. Here, we use two different diazo compounds, unsubstituted N2CH2 and donor-donor N2CPh2, with dichloromethane (CH2CI2) as the solvent. 

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