Catalytic, Regioselective 1,4-Fluorodifunctionalization of Dienes

Overview

Journal Angew Chem Int Ed Engl

Specialty Chemistry

Date 2022 Nov 8

PMID 36345795

Authors

You-Jie Yu

Michael Schafer

Constantin G Daniliuc

Ryan Gilmour

Affiliations

Soon will be listed here.

Abstract

A catalysis-based regioselective 1,4-fluorofunctionalization of trifluoromethyl substituted 1,3-dienes has been developed to access compact, highly functionalized products. The process allows E,Z-mixed dienes to be processed to a single E-alkene isomer, and leverages an inexpensive and operationally convenient I(I)/I(III) catalysis platform. The first example of catalytic 1,4-difluorination is disclosed and subsequently evolved to enable 1,4-hetero-difunctionalization, which allows δ-fluoro-alcohol and amine derivatives to be forged in a single operation. The protocol is compatible with a variety of nucleophiles including fluoride, nitriles, carboxylic acids, alcohols and even water thereby allowing highly functionalized products, with a stereocenter bearing both C(sp )-F and C(sp )-CF groups, to be generated rapidly. Scalability (up to 3 mmol), and facile post-reaction modifications are demonstrated to underscore the utility of the method in expanding organofluorine chemical space.

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