Direct Access to β‐Fluorinated Aldehydes by Nitrite‐Modified Wacker Oxidation. Issue 29 (25th May 2016)

• Record Type: Journal Article
• Authors: Chu, Crystal K.; Ziegler, Daniel T.; Carr, Brian; Wickens, Zachary K.; Grubbs, Robert H.
• Is Part Of: Angewandte Chemie international edition. Volume 55:Issue 29(2016)
• Page Start: 8435
• Page End: 8439
• Publication Date: 2016-05-25
• Subjects: aldehydes -- fluorine -- oxidation -- palladium -- regioselectivity; Chemistry -- Periodicals; 540
• DOI: 10.1002/anie.201603424
• Languages: English
• ISSNs: 1433-7851

Abstract

Abstract: 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. Abstract : Out of Wack(er) : The aldehyde‐selective Wacker‐type oxidation of allylic fluorides was accomplished using catalytic nitrite, thus providing a direct route to β‐fluorinated aldehydes. Allylic fluorides bearing a variety of functional groups are transformed in high yield and regioselectivity. Preliminary mechanistic investigations suggest that inductive effects have a strong influence on the rate and regioselectivity of the oxidation.