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Direct Access to β‐Fluorinated Aldehydes by Nitrite‐Modified Wacker Oxidation
Author(s) -
Chu Crystal K.,
Ziegler Daniel T.,
Carr Brian,
Wickens Zachary K.,
Grubbs Robert H.
Publication year - 2016
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.201603424
Subject(s) - regioselectivity , allylic rearrangement , aldehyde , chemistry , wacker process , catalysis , yield (engineering) , nitrite , organic chemistry , combinatorial chemistry , palladium , materials science , nitrate , metallurgy
An aldehyde‐selective Wacker‐type oxidation of allylic fluorides proceeds with a nitrite catalyst. The method represents a direct route to prepare β‐fluorinated aldehydes. Allylic fluorides bearing a variety of functional groups are transformed in high yield and very high regioselectivity. Additionally, the unpurified aldehyde products serve as versatile intermediates, thus enabling access to a diverse array of fluorinated building blocks. Preliminary mechanistic investigations suggest that inductive effects have a strong influence on the rate and regioselectivity of the oxidation.