Expanding the synthesizable multisubstituted benzo[b]thiophenes via 6,7-thienobenzynes generated from o-silylaryl triflate-type precursors

Yoshida, Suguru; Kuribara, Tomoko; Morita, Takamoto; Matsuzawa, Tsubasa; Morimoto, Kazushi; Kobayashi, Takuya; Hosoya, Takamitsu

doi:10.1039/c8ra04035d

Cited by 17 publications

(10 citation statements)

References 60 publications

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“…In 2018, Yoshida, Hosoya, and co-workers reported the preparation of a series of 2,3disubstituted 6,7-thienobenzyne precursors 12-74 (Scheme 289b). 905 The corresponding 6,7-thienobenzynes 12-75 could be trapped by arynophiles, furnishing the desired products 12-76 in modest C6 regioselectivity.…”

Section: 3-benzdiyne Chemistrymentioning

confidence: 99%

o-Silylaryl Triflates: A Journey of Kobayashi Aryne Precursors

2021

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Arynes are among the most active organic intermediates and have found numerous applications in expeditious preparation of substituted arenes. In the past 20 years, chemists have witnessed a resurgence in aryne chemistry, which is mainly attributed by the extensive utilization of Kobayashi's method, a fluoride-induced removal of the TMS group with concomitant departure of its ortho OTf group on o-silylaryl triflates. Nowadays, o-silylaryl triflates are the most frequently employed aryne precursors. This review provides an overview of the history of Kobayashi's method, its methodological achievements, and its applications in the synthesis of natural products, bioactive molecules, and polycyclic aromatic hydrocarbons.

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Section: 3-benzdiyne Chemistrymentioning

confidence: 99%

o-Silylaryl Triflates: A Journey of Kobayashi Aryne Precursors

2021

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“…Trisubstituted benzo[ b ]thiophenes 62 q and 62 r could be obtained from the corresponding aryne precursors. o ‐Silylaryl triflates bearing benzothiophene or phenanthrene gave the π‐conjugated 62 s and 62 t in moderate yields [71] . This synthetic method for benzo[ b ]thiophenes showed some advantages like high yields and broad substrance scope.…”

Section: Formations Of Fused‐cycles From Thioalkynesmentioning

confidence: 93%

“…o-Silylaryl triflates bearing benzothiophene or phenanthrene gave the π-conjugated 62 s and 62 t in moderate yields. [71] This synthetic method for benzo [b]thiophenes showed some advantages like high yields and broad substrance scope.…”

Section: Formation Of Benzo-cycles From Thioalkynesmentioning

confidence: 99%

Thioalkynes in Ring Forming Reactions

Peng,

Yuan,

Tang

et al. 2023

The Chemical Record

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Organic cycles play an important role in chemistry, pharmacology and material science for their unique properties. Construction of organic cycles from thioalkynes attracted increasing attention due to the facile access of thioalkynes. 2H‐Azirines were synthesized successfully from thioalkynyl oxime ethers. Cyclobutanes were formed through chiral titanium catalyzed cycloaddition of thioalkynes. Cyclopentenes were afforded by annulation of thioalkynes. Thioalkynes could be also applied to synthesize thiophenes, oxazoles, benzo[b]thiophenes, 2H‐chromenes, 2‐phenylbenzothiazoles, diazacyclobutene, etc. In this review, construction of organic cycles from thioalkynes were highlighted. Firstly, the property and application of organic cyclic compounds were simply introduced. After presenting the general methods to access organic cycles, applications of thioalkynes as synthons to prepare organic cycles were classified and presented in detail. Based on different kinds of organic cycles obtained from thioalkynes, organic reactions for synthesis of three‐, four‐, five‐, six‐membered as well as fused cycles would be summarized and the plausible reaction mechanisms could be presented if available.

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“…Since the diaryl ketone synthesis proceeded leaving a wide variety of transformable functional groups unreacted by virtue of mild reaction conditions, a wide variety of multi‐substituted benzo[ b ]thiophenes 11 , 12 , 14 , and 15 were easily prepared through aryne reactions and C−S transformations (Figure A) . Indeed, we succeeded in the synthesis of naphthothiophene 11 and triazole‐fused benzothiophene 12 via the generation of thienobenzyne VI at the o ‐iodoaryl triflate moiety and following [2+4] and [2+3] cycloadditions without damaging the carbonyl groups . Furthermore, the remarkable transformability of the methylthio group accomplished C−C bond‐forming reactions .…”

Section: Figurementioning

confidence: 99%

Synthesis of Diverse Aromatic Ketones through C−F Cleavage of Trifluoromethyl Group

Ikeda

Matsuzawa

Morita

et al. 2020

Chemistry A European J

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An efficient synthetic method of aromatick etones through CÀFc leavage of trifluoromethylg roup is disclosed. The highf unctional group tolerance of the transformationa nd the remarkable stabilityo ft rifluoromethylg roup in various reactions enabledm ulti-substituted aromatic ketone synthesis in an efficient route involving useful transformationss uch as ortho-lithiation,a ryne chemistry,a nd cross-couplings.

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Expanding the synthesizable multisubstituted benzo[b]thiophenes via 6,7-thienobenzynes generated from o-silylaryl triflate-type precursors

Abstract: Various multisubstituted benzothiophenes, including those with various heteroatom substituents and EP4 antagonist analogs, have been prepared easily via 6,7-thienobenzynes generated from o-silylaryl triflate-type precursors.

Cited by 17 publications

References 60 publications

o-Silylaryl Triflates: A Journey of Kobayashi Aryne Precursors

o-Silylaryl Triflates: A Journey of Kobayashi Aryne Precursors

Thioalkynes in Ring Forming Reactions

Synthesis of Diverse Aromatic Ketones through C−F Cleavage of Trifluoromethyl Group

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