826-66-4Relevant academic research and scientific papers
Acylstannanes: Cleavable and Highly Reactive Photoinitiators for Radical Photopolymerization at Wavelengths above 500 nm with Excellent Photobleaching Behavior
Mitterbauer, Moritz,Knaack, Patrick,Naumov, Sergej,Markovic, Marica,Ovsianikov, Alexandr,Moszner, Norbert,Liska, Robert
, p. 12146 - 12150 (2018)
Within this work, a novel acylstannane-based photoinitiator (PI) is presented. Tetrakis(2,4,6-trimethylbenzoyl)stannane (1) displays outstanding properties compared to state-of-the-art acylgermane-based initiators. Most importantly, the initiator shows absorption up to 550 nm, which allows higher penetration depths, especially in highly filled photopolymers. Besides that, 1 shows extremely high photoinitiating activity towards (meth)acrylic double bonds, as well as very fast photobleaching. Furthermore, unlike many organotin compounds, 1 shows surprisingly low cytotoxicity.
CsF-Catalyzed Fluoroacylation of Tetrafluoroethylene Using Acyl Fluorides for the Synthesis of Pentafluoroethyl Ketones
Ishida, Naoyoshi,Iwamoto, Hiroaki,Sunagawa, Denise Eimi,Ohashi, Masato,Ogoshi, Sensuke
supporting information, p. 3137 - 3143 (2020/11/13)
A catalytic method for the synthesis of pentafluoroethyl ketones has been developed. The cesium fluoride catalyst can be used to convert acyl fluorides into the pentafluoroethyl ketones under tetrafluoroethylene pressure without generating stoichiometric
Radical-Mediated Activation of Esters with a Copper/Selectfluor System: Synthesis of Bulky Amides and Peptides
Matsumoto, Akira,Wang, Zhe,Maruoka, Keiji
, p. 5401 - 5411 (2021/04/12)
Herein, we describe a new approach for the activation of esters via a radical-mediated process enabled by a copper/Selectfluor system. A variety of para-methoxybenzyl esters derived from bulky carboxylic acids and amino acids can be easily converted into the corresponding acyl fluorides, directly used in the one-pot synthesis of amides and peptides. As a proof of concept, this method was applied to the iterative formation of sterically hindered amide bonds.
Methoxylation of Acyl Fluorides with Tris(2,4,6-trimethoxyphenyl)phosphine via C-OMe Bond Cleavage under Metal-Free Conditions
Ishida, Takumi,Nishihara, Yasushi,Wang, Xiu,Wang, Zhenhua
, p. 7526 - 7533 (2020/06/27)
Acyl fluorides are subjected to methoxylation with tris(2,4,6-trimethoxyphenyl)phosphine (TMPP) to afford the corresponding methyl esters in good to excellent yields. This transformation is featured by C(sp2)-OMe bond cleavage under metal-free conditions. Unprecedented utilization of TMPP as a methoxylating agent realized the installation of an OMe group into the desired products.
Efficient cleavage of tertiary amide bonds: Via radical-polar crossover using a copper(ii) bromide/Selectfluor hybrid system
Maruoka, Keiji,Matsumoto, Akira,Wang, Zhe
, p. 12323 - 12328 (2020/12/08)
A novel approach for the efficient cleavage of the amide bonds in tertiary amides is reported. Based on the selective radical abstraction of a benzylic hydrogen atom by a CuBr2/Selectfluor hybrid system followed by a selective cleavage of an N-C bond, an acyl fluoride intermediate is formed. This intermediate may then be derivatized in a one-pot fashion. The reaction proceeds under mild conditions and exhibits a broad substrate scope with respect to the tertiary amide moiety as well as to nitrogen, oxygen, and carbon nucleophiles for the subsequent derivatization. Mechanistic studies suggest that the present reaction proceeds via a radical-polar crossover process that involves benzylic carbon radicals generated by the selective radical abstraction of a benzylic hydrogen atom by the CuBr2/Selectfluor hybrid system. Furthermore, a synthetic application of this method for the selective cleavage of peptides is described. This journal is
Sulfur–Fluoride Exchange (SuFEx)-Mediated Synthesis of Sterically Hindered and Electron-Deficient Secondary and Tertiary Amides via Acyl Fluoride Intermediates
Smedley, Christopher J.,Barrow, Andrew S.,Spiteri, Christian,Giel, Marie-Claire,Sharma, Pallavi,Moses, John E.
supporting information, p. 9990 - 9995 (2017/08/01)
Amide bond formation is one of the most executed reactions in chemistry and biology. This is largely due to the ubiquity of the amide functional group in biological molecules, natural products and pharmaceutically important drugs. We report here the development of “SuFExAmide”: a new sulfur–fluoride exchange (SuFEx) click chemistry based protocol for the efficient amidation of carboxylic acids via acyl fluoride intermediates. We have developed benzene-1,3-disulfonyl fluoride as a cost effective, powerful and versatile coupling agent, which delivers challenging secondary and tertiary amides in excellent yields from sterically hindered and electron-deficient amines. The straightforward method offers significant benefits over existing protocols in terms of substrate scope, efficiency and ease of operation and is demonstrated by the synthesis of 44 amides, including GNF6702, an antiprotozoal drug candidate. In the majority of cases, the amide products are obtained in high yield without the need for excess reagents or chromatographic purification.
A protocol for amide bond formation with electron deficient amines and sterically hindered substrates
Due-Hansen, Maria E.,Pandey, Sunil K.,Christiansen, Elisabeth,Andersen, Rikke,Hansen, Steffen V. F.,Ulven, Trond
supporting information, p. 430 - 433 (2016/01/12)
A protocol for amide coupling by in situ formation of acyl fluorides and reaction with amines at elevated temperature has been developed and found to be efficient for coupling of sterically hindered substrates and electron deficient amines where standard methods failed.
