Synthesis of fluorinated amphoteric organoborons via iodofluorination of alkynyl and alkenyl MIDA boronates

Abstract

The iodofluorination of alkynyl and alkenyl MIDA boronates led to the synthesis of fluorinated organoborons bearing a valuable C–I bond.

Regiocontrolled allylic functionalization of internal alkene via selenium-π-acid catalysis guided by boron substitution

“…A copper-catalyzed displacement of chloride furnished an allyl fluoride 7 without difficulty. 21 In addition, the iodofluorination of the double bond in 2a following our previous protocol 22 produced the α-iodo-β-fluoro-γ-chloroalkyl MIDA boronate 8 (confirmed by X-ray single crystal diffraction analysis) 23 with good regio- and stereoselectivity. And the epoxidation reaction gave efficiently a highly functionalized amphoteric epoxide 9 .…”

Hypervalent iodine-mediated β-difluoroalkylboron synthesis via an unusual 1,2-hydrogen shift enabled by boron substitution

“…The regioselectivity could arise from an electron-donating inductive effect from boron due to its low electronegativity, consistent with previous observations. 13 a , b Thereafter, a 1,2-hydrogen shift, rather than the typical direct fluoride substitution of the C–I bond, provides carbon cation C. The formation of a hyperconjugatively stabilized cation is believed to be the driving force for this event. 12 a – d The trapping of this cation finally forms the product.…”

Regiocontrolled Allylic Functionalization of Internal Alkene via Selenium-pi-Acid Catalysis Guided by Boron Substitution

“…A copper-catalyzed displacement of chloride furnished an allyl fluoride 7 without difficulty. 21 In addition, the iodofluorination of the double bond in 2a following our previous protocol 22 produced the α-iodo-β-fluoro-γ-chloroalkyl MIDA boronate 8 (confirmed by X-ray single crystal diffraction analysis) 23 Finally, the transesterification reaction of the BMIDA moiety with pinacol allowed the efficient synthesis of alkenyl Bpin 10. And under a slow-release reaction conditions, the palladium-catalyzed Suzuki-Miyaura coupling with aryl iodide was successful to provide the styrenyl product 5.…”