1253786-03-6Relevant articles and documents
Acylalkylation of Arynes Generated from o-Iodoaryl Triflates with Hydrosilanes and Cesium Fluoride
Minoshima, Mai,Uchida, Keisuke,Nakamura, Yu,Hosoya, Takamitsu,Yoshida, Suguru
supporting information, p. 1868 - 1873 (2021/03/08)
An efficient method to generate aryne intermediates from o-iodoaryl triflates triggered by triethylsilane and cesium fluoride is disclosed. This method realized the acylalkylation of arynes using easily available o-iodoaryl triflate-type precursors, which was difficult when using conventional nucleophilic activators. A wide range of (hetero)arenes including various fused benzothiazoles were successfully synthesized from o-iodoaryl triflates by virtue of their good accessibility and divergent transformations of aryne intermediates.
One-Pot Generation of Functionalized Benzynes from Readily Available 2-Hydroxyphenylboronic Acids
Ikawa, Takashi,Sun, Jingkai,Takagi, Akira,Akai, Shuji
, p. 3383 - 3392 (2020/03/10)
We developed a one-pot method for the generation of benzynes from a range of readily available 2-hydroxyphenylboronic acids. This method features the in situ activation of both boronic acid and hydroxyl groups of the substrate to enhance benzyne generation at 60 °C. Such mild conditions facilitate the generation of functionalized benzynes that immediately react with diverse arynophiles to produce multisubstituted fused benzenes.
Arynes and Their Precursors from Arylboronic Acids via Catalytic C-H Silylation
Devaraj, Karthik,Ingner, Fredric J.L.,Sollert, Carina,Gates, Paul J.,Orthaber, Andreas,Pilarski, Lukasz T.
, p. 5863 - 5871 (2019/04/16)
A new, operationally simple approach is presented to access arynes and their fluoride-activated precursors based on Ru-catalyzed C-H silylation of arylboronates. Chromatographic purification may be deferred until after aryne capture, rendering the arylboronates de facto precursors. Access to various new arynes and their derivatives is demonstrated, including, for the first time, those based on a 2,3-carbazolyne and 2,3-fluorenyne core, which pave the way for novel derivatizations of motifs relevant to materials chemistry.
Generation of arynes by selective cleavage of a carbonphosphorus bond of o-(diarylphosphinyl)aryl triflates using a grignard reagent
Nishiyama, Yoshitake,Kamada, Shuhei,Yoshida, Suguru,Hosoya, Takamitsu
, p. 1216 - 1219 (2018/09/11)
A novel method for generating arynes, including disubsti-tuted benzynes and a dehydrophenoxathiin, is reported. The treatment of easily synthesizable o-(diarylphosphinyl)aryl triflates having two electron-deficient aromatic groups on the phosphorus atom with a phenyl Grignard reagent triggered the efficient generation of arynes by selective cleavage of a carbonphosphorus bond.
2-(Trimethylsilyl)phenyl Trimethylsilyl Ethers as Stable and Readily Accessible Benzyne Precursors
Ikawa, Takashi,Masuda, Shigeaki,Nakajima, Hiroki,Akai, Shuji
, p. 4242 - 4253 (2017/04/27)
Stable 2-(trimethylsilyl)phenyl trimethylsilyl ethers, readily obtained from the corresponding halogenated phenols in two steps, were identified as novel benzyne precursors. These species were converted to benzynes by a domino reaction of O-desilylation,
Generation of arynes triggered by sulfoxidemetal exchange reaction of ortho-sulfinylaryl triflates
Yoshida, Suguru,Uchida, Keisuke,Hosoya, Takamitsu
, p. 116 - 118 (2014/01/23)
Arynes were efficiently generated from readily available ortho-sulfinylaryl triflates by the treatment with phenylmagnesium bromide in tetrahydrofuran at 78 C. Aryne generation was initiated by a rapid sulfoxidemetal exchange reaction, followed by the immediate elimination of the ortho-OTf group. Various arynophiles efficiently reacted with arynes generated by this method within 10min, providing the corresponding adducts in high yields.
Generation of arynes via ate complexes of arylboronic esters with an ortho-leaving group
Sumida, Yuto,Kato, Tomoe,Hosoya, Takamitsu
supporting information, p. 2806 - 2809 (2013/07/11)
An efficient method of generating aryne has been achieved by treating ortho-(trifluoromethanesulfonyloxy)arylboronic acid pinacol ester with tert- or sec-butyllithium. Monitoring the reaction by 11B NMR has indicated that a boron-ate complex formed in situ is the eventual precursor that converts into aryne near room temperature. The prior formation of the ate complex at a low temperature has enabled us to use various arynophiles, including those bearing base-sensitive groups. The ready availability of the aryne precursors and mutual orthogonality in aryne generation with widely used ortho-silylaryl triflate have enhanced the utility of the method.
Synthesis of dihydrobenzisoxazoles by the [3 + 2] cycloaddition of arynes and oxaziridines
Kivrak, Arif,Larock, Richard C.
experimental part, p. 7381 - 7387 (2011/02/22)
Dihydrobenzisoxazoles are readily prepared in good yields by the [3 + 2] cycloaddition of oxaziridines and arynes. The reaction involves an unusual cleavage of the C-O bond of the oxaziridine and tolerates a variety of substituents on the oxaziridine and the o-(trimethylsilyl)aryl triflate to form aryl-, heteroaryl-, alkyl-, and naphthyl-substituted dihydrobenzisoxazoles. The resulting halogen-substituted dihydrobenzisoxazoles are readily elaborated to more complex products using palladium-catalyzed crossing-coupling processes.
