- Photoinitiated Reactions of Haloperfluorocarbons with Gold(I) Organometallic Complexes: Perfluoroalkyl Gold(I) and Gold(III) Complexes
-
The study of perfluoroalkyl metal complexes is key to understand and improve metal-promoted perfluoroalkylation reactions. Herein, we report the synthesis of the first gold complexes with primary or secondary perfluoroalkyl ligands by photoinitiated reactions between AuI organometallic complexes and iodoperfluoroalkanes. Complexes of the types LAuRF (L=PPh3 or N,N-bis(2,6-diisopropylphenyl)imidazol-2-ylidene; RF=n-C4F9, n-C6F13, i-C3F7, c-C6F11) and [Au(RF)(Ar)I(PPh3)] (Ar=2,4,6-trimethylphenyl) have been isolated and characterized. Alkynes RFC≡CR were formed by reaction of Ph3PAuC≡CR (R=Ph, nHex) with IRF (RF=n-C4F9, i-C3F7). According to the evidences obtained, this transformation undergoes through a photoinitiated radical mechanism. AuIII complexes [Au(n-C4F9)(X)(Y)L] (X=Y=Cl, Br, I, Me; X=Me, Y=I) have been prepared or in situ generated, and their thermal or photochemical decomposition reactions have been studied.
- Portugués, Alejandro,López-García, Inmaculada,Jiménez-Bernad, Javier,Bautista, Delia,Gil-Rubio, Juan
-
-
Read Online
- Perfluoroalkylation of Terminal Alkynes with Perfluoroalkyl Iodides Catalyzed by an Iron Salt
-
The one-step, direct perfluoroalkylation of terminal alkynes with perfluoroalkyl iodides has been developed in which a simple ligandless iron salt is employed as the catalyst. Various perfluoroalkylated alkynes could be afforded in good to excellent yields with good functional group compatibility. Preliminary mechanistic studies suggest the involvement of the perfluoroalkyl radical in the catalytic cycle and the perfluoroalkylated alkenyl iodides as intermediates. The method provides straight, streamlined, and sustainable access to perfluoroalkylated acetylenes.
- Li, Hengyuan,Li, Huaifeng,Li, Wei,Li, Xiaofeng,Liang, Changfa,Luo, Baogui,Wang, Zhenhui,Yang, Huanjian
-
supporting information
p. 1554 - 1558
(2022/01/20)
-
- Copper-Catalyzed Perfluoroalkylation of Alkynyl Bromides and Terminal Alkynes
-
A copper-catalyzed one-pot perfluoroalkylation of alkynyl bromides and terminal alkynes has been disclosed, and the corresponding perfluoroalkylated alkynes could be attained in good to excellent yields. The new straightforward transformation shows high efficiency (0.01-0.5 mol % catalyst loading), broad substrate scope, and remarkable functional group tolerance and provides a facile approach for useful application in life and material sciences.
- Fan, Shilu,Zheng, Chenggong,Zheng, Kaiting,Li, Junlan,Liu, Yaomei,Yan, Fangpei,Xiao, Hua,Feng, Yi-Si,Zhu, Yuan-Yuan
-
supporting information
p. 3190 - 3194
(2021/05/05)
-
- Visible light photocatalytic cross-coupling and addition reactions of arylalkynes with perfluoroalkyl iodides
-
Visible light photocatalytic cross-coupling and addition reactions of arylalkynes with perfluoroalkyl iodides have been developed. Through slight modifications of the reaction conditions, reactions that are selective for the preparation of the C-C couplin
- Cheng, Shun-Cheung,Chun, Yuen-Kiu,Ko, Chi-Chiu,Liu, Ruoyang,Tse, Man-Kit,Xiao, Yelan
-
p. 8686 - 8693
(2020/11/17)
-
- Silver-Mediated Perfluoroalkylation of Terminal Alkynes with Perfluoroalkyl Iodides
-
The incorporation of a perfluoroalkyl group (RF) into drug candidates has become an increasingly important strategy in drug molecule design. In this study, the silver-mediated perfluoroalkylation reaction based on the addition-elimination process of terminal alkynes which was initiated by a perfluoroalkyl radical to form a C(sp)-RF bond has been developed. The reaction proceeds under mild conditions using readily available, low-cost perfluoroalkyl iodides as the sources of the RF group. This method allows access to a variety of perfluoroalkylated alkynes.
- Li, Junlan,Liu, Lihua,Zheng, Kaiting,Zheng, Chenggong,Xiao, Hua,Fan, Shilu
-
p. 8723 - 8731
(2020/09/07)
-
- Synthesis of fluoroalkylated alkynes: Via visible-light photocatalysis
-
Fluoroalkylated alkynes, which are versatile building blocks for the synthesis of various biologically active organofluorine compounds, were synthesized from easily available alkynyl halides and fluoroalkyl halides by visible-light photocatalysis. Addition of fluoroalkyl radicals to alkynes and subsequent dehalogenation selectively yielded fluoroalkylated alkynes.
- Iqbal, Naila,Iqbal, Naeem,Han, Sung Su,Cho, Eun Jin
-
p. 1758 - 1762
(2019/02/20)
-
- Facile syntheses of various per- or polyfluoroalkylated internal acetylene derivatives
-
Treatment of per- or polyfluoroalkylated vinyl iodides 5 with 2equiv. of n-BuLi in THF produced the corresponding lithium acetylides in situ, which were transformed into zinc acetylides by the addition of ZnCl2· TMEDA complex into the reaction mixture. The in situ generated zinc acetylides were exposed to the cross-coupling conditions such as ArI/cat. Pd(PPh 3)4, reflux, 6-12 h, giving rise to the desired per- or polyfluoroalkylated acetylenes in high yields. In the case of trifluoromethylated acetylene, commercially available 2-bromo-3,3,3-trifluoropropene 6 could also be used instead of 5 as the starting material. In the acetylenes having a fluoroalkyl group and an aliphatic side chain, vinyl iodides 7, prepared by radical addition of perfluoroalkyl iodide to terminal acetylenes, were treated with t-BuOK at room temperature or at the reflux temperature of benzene, affording the desired compounds in good yields.
- Konno, Tsutomu,Chae, Jungha,Kanda, Masashi,Nagai, Go,Tamura, Kazushige,Ishihara, Takashi,Yamanaka, Hiroki
-
p. 7571 - 7580
(2007/10/03)
-