Highly selective photoinduced perfluoroalkylation of vinylsilanes and its application to synthesis of water-shedding polysilanes

Abstract

The functionalization of polysilanes is an important subject in materials science because functionalized polysilanes are expected to exhibit potentially innovative properties. This research aims at the addition of a water-shedding property to polysilanes by introducing perfluoroalkyl groups into their skeleton. The photoinduced iodoperfluoroalkylation of various vinylsilanes takes place successfully upon irradiation with a xenon lamp: vinylmonosilanes undergo iodoperfluoroalkylation with perfluoroalkyl iodides (R f I) regioselectively, and the corresponding perfluoroalkylated silanes are obtained in moderate to high yields. Detailed optimization of the photoinduced iodoperfluoroalkylation has been investigated to apply this method to the functionalization of polysilanes. Polysilanes having vinyl groups can be synthesized by the reductive coupling of dichlorovinylsilanes with samarium diiodide (SmI 2 ) and samarium metal (Sm) upon irradiation with visible light. The synthesized vinylpolysilanes and R f I (about 1.0 mM CHCl 3 solution) are coated on a glass plate sequentially, and then the following photoirradiation with light of a wavelength over 300 nm successfully adds an excellent water-shedding property to the glass plate.

Fluoroalkyl Iodides in Fluoroalkylative Difunctionalization of C−C Multiple Bonds

“…Despite the fact that direct photolysis of IR F is achievable using high intensity UV lamps (250-320 nm), [51][52][53][54][55] recently several methodologies have been developed to perform the transformation using cheaper and less harmful visible light sources, most typically blue LEDs. Two strategies have been employed to reach this goal: 1) photoredox catalysis; and 2) activation of the IÀ C bond through formation of electron donor-acceptor (EDA) complexes.…”

Mechanistic Insights into FLP‐Catalyzed Iodoperfluoroalkylations

“…Consequently, the development of selective fluorination techniques is of great importance in the pharmaceutical industry. A plethora of methods for fluorination and fluoroalkylation has been described in past years involving special fluorinating reagents,[8f], diverse transition metal catalysts, metal‐free alternatives involving amines as Lewis base catalysts, or photo‐mediated perfluoroalkylations , . However, enantioselective methods and late stage introduction of fluorine is still a crucial goal.…”

Application of Bifunctional 2-Amino-1,4-naphthoquinones in Visible-Light-Promoted Photocatalyst-Free Alkene Perfluoroalkyl-Alkenylation

“…As the most common perfluoroalkyl source, perfluoroalkyl iodides present their absorption in UV or near-UV zones . They are usually activated to generate perfluoroalkyl radicals by organic radical initiators or ultraviolet irradiation. , Due to their green and economical characteristics, visible-light-promoted organic transformations have received more and more attention in recent years . Therefore, visible-light-promoted activation of perfluoroalkyl iodides has been achieved through perfluoroalkyl radicals in various perfluoroalkylation reactions.…”