66107-33-3Relevant articles and documents
Facile synthesis of diverse multisubstituted ortho-silylaryl triflates via CH borylation
Yoshida, Suguru,Shimomori, Ken,Nonaka, Takako,Hosoya, Takamitsu
, p. 1324 - 1326 (2015)
Diverse multisubstituted ortho-silylaryl triflates were efficiently synthesized from simple ortho-silylaryl triflates via iridium-catalyzed regioselective CH borylation and subsequent deborylative functionalizations. An azidoaryne precursor synthesized by this method served as a useful bis-reactive platform molecule, thus demonstrating the utility of the method for preparing diverse aromatic compounds.
Base-promoted selective O-phosphorylation of aryl triflates with P(O)-H compounds
Wang, Mingyue,Yang, Jia,Wang, Shuai,Zhong, Hong
supporting information, (2020/05/05)
Compared to previous transition metal-catalyzed C-phosphorylation reactions for constructing C–P bonds, in the absence of transition metal catalysts and ligands, a direct O-phosphorylation of aryl triflates selectively occurred with P(O)-H compounds in the presence of a base via the construction of O–P bonds. This transformation proceeds under simple and mild conditions, and provides a new method for the preparation of valuable organophosphoryl compounds from readily available P(O)-H compounds and triflates.
Bismuth-Catalyzed Oxidative Coupling of Arylboronic Acids with Triflate and Nonaflate Salts
Cornella, Josep,Peciukenas, Vytautas,Planas, Oriol
supporting information, p. 11382 - 11387 (2020/07/14)
Herein we present a Bi-catalyzed cross-coupling of arylboronic acids with perfluoroalkyl sulfonate salts based on a Bi(III)/Bi(V) redox cycle. An electron-deficient sulfone ligand proved to be key for the successful implementation of this protocol, which allows the unusual construction of C(sp2)-O bonds using commercially available NaOTf and KONf as coupling partners. Preliminary mechanistic studies as well as theoretical investigations reveal the intermediacy of a highly electrophilic Bi(V) species, which rapidly eliminates phenyl triflate.
Ni-Catalyzed Reductive Cyanation of Aryl Halides and Phenol Derivatives via Transnitrilation
Mills, L. Reginald,Graham, Joshua M.,Patel, Purvish,Rousseaux, Sophie A. L.
supporting information, p. 19257 - 19262 (2019/12/02)
Herein, we report a Ni-catalyzed reductive coupling for the synthesis of benzonitriles from aryl (pseudo)halides and an electrophilic cyanating reagent, 2-methyl-2-phenyl malononitrile (MPMN). MPMN is a bench-stable, carbon-bound electrophilic CN reagent that does not release cyanide under the reaction conditions. A variety of medicinally relevant benzonitriles can be made in good yields. Addition of NaBr to the reaction mixture allows for the use of more challenging aryl electrophiles such as aryl chlorides, tosylates, and triflates. Mechanistic investigations suggest that NaBr plays a role in facilitating oxidative addition with these substrates.
Transition-Metal-Free C-C, C-O, and C-N Cross-Couplings Enabled by Light
Liu, Wenbo,Li, Jianbin,Querard, Pierre,Li, Chao-Jun
supporting information, p. 6755 - 6764 (2019/05/06)
Transition-metal-catalyzed cross-couplings to construct C-C, C-O, and C-N bonds have revolutionized chemical science. Despite great achievements, these metal catalysts also raise certain issues including their high cost, requirement of specialized ligands, sensitivity to air and moisture, and so-called "transition-metal-residue issue". Complementary strategy, which does not rely on the well-established oxidative addition, transmetalation, and reductive elimination mechanistic paradigm, would potentially eliminate all of these metal-related issues. Herein, we show that aryl triflates can be coupled with potassium aryl trifluoroborates, aliphatic alcohols, and nitriles without the assistance of metal catalysts empowered by photoenergy. Control experiments reveal that among all common aryl electrophiles only aryl triflates are competent in these couplings whereas aryl iodides and bromides cannot serve as the coupling partners. DFT calculation reveals that once converted to the aryl radical cation, aryl triflate would be more favorable to ipso substitution. Fluorescence spectroscopy and cyclic voltammetry investigations suggest that the interaction between excited acetone and aryl triflate is essential to these couplings. The results in this report are anticipated to provide new opportunities to perform cross-couplings.
Solvent-free ruthenium-catalysed triflate coupling as a convenient method for selective azole-o-C-H monoarylation
Abidi, Oumaima,Boubaker, Taoufik,Hierso, Jean-Cyrille,Roger, Julien
supporting information, p. 5916 - 5919 (2019/06/24)
Metal-catalysed ortho-directed C-H functionalization usually faces selectivity issues in the competition between mono- and disubstitution processes. We report herein the ruthenium-catalysed N-directed C-H monoarylation of arylpyrazoles with a selectivity
ortho-Difunctionalization of arynes by LiZnEt2(TMP)-mediated deprotonative zincation/elimination of aryl triflates
Cho, Seoyoung,Wang, Qiu
supporting information, p. 3325 - 3328 (2018/04/02)
Generation of arynes from aryl triflates has been achieved using lithium diethyl(tetramethylpiperidyl)-zincate base LiZnEt2(TMP), via a directed ortho-deprotonative zincation and subsequent elimination of the triflate group. The aryne formation
The Directed ortho Metalation (D o M)-Cross-Coupling Connection: Synthesis of Polyfunctional Biaryls
Quesnelle, Claude A.,Snieckus, Victor
supporting information, p. 4413 - 4428 (2018/11/21)
A comparative evaluation of the combined directed ortho metalation (D o M)-Suzuki-Miyaura and D o M-Negishi cross-coupling reactions with aryl triflates for the synthesis of substituted biaryls is described. Both ortho -zinc and ortho -boron aryl directed
A Heck-Based Strategy to Generate Anacardic Acids and Related Phenolic Lipids for Isoform-Specific Bioactivity Profiling
Weigel, William K.,Dennis, Taylor N.,Kang, Amrik S.,Perry, J. Jefferson P.,Martin, David B. C.
supporting information, p. 6234 - 6238 (2018/10/05)
A synthetic strategy for phenolic lipids such as anacardic acid and ginkgolic acid derivatives using an efficient and selective redox-relay Heck reaction followed by a stereoselective olefination is reported. This approach controls both the alkene position and stereochemistry, allowing the synthesis of natural and unnatural unsaturated lipids as single isomers. By this strategy, the activities of different anacardic acid and ginkgolic acid derivatives have been examined in a matrix metalloproteinase inhibition assay.
Reactions of Arylsulfonate Electrophiles with NMe4F: Mechanistic Insight, Reactivity, and Scope
Schimler, Sydonie D.,Froese, Robert D. J.,Bland, Douglas C.,Sanford, Melanie S.
, p. 11178 - 11190 (2018/09/12)
This paper describes a detailed study of the deoxyfluorination of aryl fluorosulfonates with tetramethylammonium fluoride (NMe4F) and ultimately identifies other sulfonate electrophiles that participate in this transformation. 19F NMR spectroscopic monitoring of the deoxyfluorination of aryl fluorosulfonates revealed the rapid formation of diaryl sulfates under the reaction conditions. These intermediates can proceed to fluorinated products; however, diaryl sulfate derivatives bearing electron-donating substituents react very slowly with NMe4F. Based on these findings, aryl triflate and aryl nonaflate derivatives were explored, since these cannot react to form diaryl sulfates. Aryl triflates were found to be particularly effective electrophiles for deoxyfluorination with NMe4F, and certain derivatives (i.e., those bearing electron-neutral/donating substituents) afforded higher yields than their aryl fluorosulfonate counterparts. Computational studies implicate a similar mechanism for deoxyfluorination of all the sulfonate electrophiles.
