Abstract
Herein we describe the first construction of fluorinated tertiary stereocenters based on an alkene C(sp2)–C(sp2) bond cleavage. The new process, that takes advantage of a Rh-catalyzed carbyne transfer, relies on a branched-selective fluorination of tertiary allyl cations and is distinguished by a wide scope including natural products and drug molecule derivatives as well as adaptability to radiofluorination.
Highlights
The growing number of approved uorinated small-molecule pharmaceuticals is a testimony of the tremendous research efforts in synthetic organo uorine chemistry[1] and their application in uorine-based drug design.[2]
As part of a research programme focused on the development of a carbyne transfer platform in organic synthesis, we reported a catalytic strategy that generates Rh-carbynoids as I(III)-substituted Rh-carbenes by selective diazo activation of bespoke hypervalent iodine reagents with a rhodium paddlewheel catalyst (Fig. 1B).[12,13]
The formation of (Æ)-3a was proposed to proceed via (i) catalytic generation of a Rh-carbynoid cation may be centered at the a position, due to the double substitution with two stabilizing groups.[14,15]
Summary
The growing number of approved uorinated small-molecule pharmaceuticals is a testimony of the tremendous research efforts in synthetic organo uorine chemistry[1] and their application in uorine-based drug design.[2]. Catalytic uorination of alkenes, allylic electrophiles, and C–H bonds with nucleophilic uoride sources represents in general an efficient option considering the availability of uoride sources.[5,6] Edge Article alkenes and permits the installation of a uorinated tertiary stereocenter in natural products and drug molecule derivatives.
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