Dyotropic Rearrangement of Tertiary Alcohols for the Synthesis of Fluorinated Tetrasubstituted Carbons

Key words

fluorination - palladium catalysis - dyotropic rearrangement

Significance

The authors report an unprecedented 1,2-aryl/Pd^IV dyotropic rearrangement along a C–O bond to generate α-fluorinated tertiary ethers. The reaction proceeds with stereoinversion of absolute configuration of the tertiary alcohol center. It is hypothesized that the driving force for the 1,2-dytropic rearrangement is the generation of a π-oxyallyl Pd^IV species.

Comment

Inclusion of a cyclopropyl group on the tertiary alcohol center indicated to the authors that radical intermediates are likely not involved. The authors were also able to carry out several post-transformations to generate a variety of fluorinated analogues of biologically active compounds.

Publication History

Article published online:
14 June 2024