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

Contributor(s):

Mark Lautens

Andrew G. Durant

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.

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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.

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Publication History

Article published online:
14 June 2024

Georg Thieme Verlag KG
Rüdigerstraße 14, 70469 Stuttgart, Germany

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