Visible light-Induced Synthesis of Perfluoroalkylated Compounds

Abstract

Synthesis of perfluorinated molecules has been of great interest since the incorporation of fluoroalkyl groups to organic molecules has a significant impact on their physical and biological properties. Visible light-induced photoredox catalysis, which has emerged as a powerful tool for organic transformations due to its environmental compatibility, allowed access to a variety of fluoroalkyl group-containing molecules, such as –CF2R, –CF3, –C3F7, and –C4F9 groups. An efficient method for the generation of CF3-containing epoxides has been developed. A variety of allylic alcohols were transformed into the corresponding epoxides by using [Ru(bpy)3]Cl2 (bpy=2,2′-bipyridine), CF3I, and 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) under visible-light irradiation at room temperature. Perfluoroalkylations by using other perfluoroalkyl iodides, such as C3F7I and C4F9I, also proceeded well under the conditions. A variety of unactivated aromatics were difluoroalkylated with BrCF2CO2Et in the presence of fac-[Ir(ppy)3] under visible light irradiation at room temperature. In addition, it was shown that reaction outcomes containing CF2CO2Et can be converted to a variety of other CF2-containing aromatics.|플루오르알킬 그룹이 유기분자에 도입되면 그 물질의 물리적, 생물학적 성질에 중요한 영향을 주기 때문에 퍼플루오르알킬 그룹을 분자내 도입하는 합성법의 개발은 매우 흥미로운 연구이다. 유기 합성분야에 환경적으로도 안정적인 특성 때문에 강력한 수단으로 개발된 가시광선을 이용한 광반응 합성법은 –CF2R, –CF3, –C3F7, 그리고 –C4F9 그룹과 같은 다양한 플루오르 알킬 그룹을 가지는 분자와의 접근을 가능하게 해준다. CF3를 포함하고 있는 에폭사이드의 합성법을 개발하였다. 다양한 종류의 치환기를 포함하고 있는 알릴릭 알코올로부터 [Ru(bpy)3]Cl2 (bpy=2,2′-bipyridine), CF3I, 그리고 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU)를 사용하여 가시광선 파장이 공급되는 조건과 함께 실온에서 에폭사이드를 합성하였다. C3F7I 과 C4F9I와 같은 다른 퍼플루오르 알킬그룹을 가지고 있는 반응 또한 위의 제시된 조건하에서 잘 진행되었다. 다양한 종류의 방향족 화합물은 가시광선과 상온, fac-[Ir(ppy)3], 그리고BrCF2CO2Et와 함께 반응하여 –CF2R그룹을 가지는 치환기를 도입할 수 있었다. 게다가, CF2CO2E는 다양한 다른 종류의 CF2를 가지는 방향족 화합물로 변환 가능하다.; Synthesis of perfluorinated molecules has been of great interest since the incorporation of fluoroalkyl groups to organic molecules has a significant impact on their physical and biological properties. Visible light-induced photoredox catalysis, which has emerged as a powerful tool for organic transformations due to its environmental compatibility, allowed access to a variety of fluoroalkyl group-containing molecules, such as –CF2R, –CF3, –C3F7, and –C4F9 groups. An efficient method for the generation of CF3-containing epoxides has been developed. A variety of allylic alcohols were transformed into the corresponding epoxides by using [Ru(bpy)3]Cl2 (bpy=2,2′-bipyridine), CF3I, and 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) under visible-light irradiation at room temperature. Perfluoroalkylations by using other perfluoroalkyl iodides, such as C3F7I and C4F9I, also proceeded well under the conditions. A variety of unactivated aromatics were difluoroalkylated with BrCF2CO2Et in the presence of fac-[Ir(ppy)3] under visible light irradiation at room temperature. In addition, it was shown that reaction outcomes containing CF2CO2Et can be converted to a variety of other CF2-containing aromatics.