Delcaillau T,
Yang B,
Wang Q,
Zhu J.
*
Ecole Polytechnique Fédérale de Lausanne, Switzerland
Editing Tetrasubstituted Carbon: Dual C–O Bond Functionalization of Tertiary Alcohols
Enabled by Palladium-Based Dyotropic Rearrangement.
J. Am. Chem. Soc. 2024;
146: 11061-11066
DOI:
10.1021/jacs.4c02924
Key words
fluorination - palladium catalysis - dyotropic rearrangement
Significance
The authors report an unprecedented 1,2-aryl/PdIV 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 PdIV 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.
