58144-49-3Relevant academic research and scientific papers
2-(Chlorodiisopropylsilyl)-6-(trimethylsilyl)phenyl triflate: A modified platform for intramolecular benzyne cycloadditions
Takasu, Kiyosei,Takikawa, Hiroshi,Tawatari, Tsukasa
supporting information, p. 11863 - 11866 (2021/11/30)
2-(Chlorodiisopropylsilyl)-6-(trimethylsilyl)phenyl triflate serves as an efficient aryne precursor for intramolecular benzyne [4 + 2] or (2 + 2 + 2) cycloadditions. Key features of this precursor are (1) rapid connection of various arynophiles to the pre
Mild synthesis of triarylsulfonium salts with arynes
Zhang, Lei,Li, Xiaojin,Sun, Yan,Zhao, Weizhao,Luo, Fan,Huang, Xin,Lin, Lihui,Yang, Ying,Peng, Bo
supporting information, p. 7181 - 7189 (2017/09/07)
Reactions between arynes and alkyl sulfides have been extensively studied over the past few decades. These reactions commonly end with a dealkylation process and thus deliver thioethers as final products. In contrast, the transformation described furnishes valuable triarylsulfonium salts, in lieu of thioethers, from arynes and diarylsulfides. The reaction features mild conditions and a broad substrate scope. A suite of functional groups such as ketones, esters, nitriles, aryl ethers and aryl halides is tolerated, which can be issues faced by traditional synthetic methods. The practicality of the reaction and its extension to the synthesis of triphenyl selenonium salt are also exhibited herein.
Continuous-flow synthesis of trimethylsilylphenyl perfluorosulfonate benzyne precursors
Michel, Boris,Greaney, Michael F.
supporting information, p. 2684 - 2687 (2014/06/09)
2-(Trimethylsilyl)phenyl perfluorosulfonated aryne precursors may now be accessed using flow chemistry, enabling the fast preparation of pure compounds with no requirement for low temperature lithiation or column chromatography. The process has been adapted to novel nonaflate precursors, utilizing the cheaper and more user-friendly nonaflyl fluoride reagent. The resultant nonaflates are shown to successfully participate in a range of aryne reaction classes.
Regiocomplementary cycloaddition reactions of boryl- and silylbenzynes with 1,3-dipoles: Selective synthesis of benzo-fused azole derivatives
Ikawa, Takashi,Takagi, Akira,Goto, Masahiko,Aoyama, Yuya,Ishikawa, Yoshinobu,Itoh, Yuji,Fujii, Satoshi,Tokiwa, Hiroaki,Akai, Shuji
, p. 2965 - 2983 (2013/06/26)
Benzo-fused nitrogen-containing heterocycles are abundant in biologically active compounds. One of the most important methods for preparing such heterocycles is the (3 + 2) cycloaddition reaction of benzynes with 1,3-dipolar compounds. However, the reacti
Steric effects compete with aryne distortion to control regioselectivities of nucleophilic additions to 3-silylarynes
Bronner, Sarah M.,MacKey, Joel L.,Houk,Garg, Neil K.
supporting information, p. 13966 - 13969 (2012/10/29)
We report an experimental and computational study of 3-silylarynes. The addition of nucleophiles yield ortho-substituted products as a result of aryne distortion, but meta-substituted products form predominately when the nucleophile is large. Computations correctly predict the preferred site of attack observed in both nucleophilic addition and cycloaddition experiments. Nucleophilic additions to 3-tert-butylbenzyne, which is not significantly distorted, give meta-substituted products.
Approaches to the quaternary stereocentre and to the heterocyclic core in diazonamide A using the Heck reaction and related coupling reactions
Booker, James E. M.,Boto, Alicia,Churchill, Gwydion H.,Green, Clive P.,Ling, Matthew,Meek, Graham,Prabhakaran, Jaya,Sinclair, David,Blake, Alexander J.,Pattenden, Gerald
, p. 4193 - 4205 (2008/09/19)
In model studies towards the quaternary centre at the heart of diazonamide A (early structure 2; revised structure 1), cyclisations of the alkene-substituted iodoaryls 4, 13, 18 and 23, under Heck reaction conditions, were shown to lead to the corresponding benzodihydrofuran 5, benzofuranone 14 and the oxindoles 19 and 24 respectively, in 50-80% yield. Further manipulation of the benzodihydrofuran 5 then led to the intermediates 30, 33 and 39, which make up parts of the oxazole-indole heterocyclic core in diazonamide A. Attempts to perform a corresponding 13-exo-trig Heck cyclisation from the precursor 46a, prepared from 44 and 45, leading to 47 were not successful. A similar outcome was obtained during attempts to effect Heck cyclisations from the ester 57 and the related ether 59. Treatment of the chromene-substituted iodoaryl 62 with Pd(OAc)2, PPh3 and Ag2CO3 led to the spirocycle 64 as a crystalline solid. X-Ray crystal structure analysis established that the quaternary centre in 64 had the same configuration as that present in diazonamide A (1). The Royal Society of Chemistry 2006.
Intramolecular carbolithiation of allyl o-lithioaryl ethers: A new enantioselective synthesis of functionalized 2,3-dihydrobenzofurans
Barluenga, Jose,Fananas, Francisco J.,Sanz, Roberto,Marcos, Cesar
, p. 5397 - 5407 (2007/10/03)
A new and easy method for the diastereoselective synthesis of 3-functionalized 2,3-dihydrobenzofuran derivatives from allyl 2-bromoaryl ethers is described. The key step of this transformation involves an intramolecular carbolithiation reaction of allyl 2-lithioaryl ethers. The substituents in both the allyl and the aryl moieties play an important and decisive role in stopping the reaction at the benzofuran thus avoiding a γ-elimination reaction. Finally, this process is amenable to the synthesis of enantiomerically enriched compounds by using ( - )-sparteine as a chiral inductor.
