An Investigation on the Synthesis of New Molecular Architectures from the Cyclotrimerisation of exo‐ and endo‐Benzotricyclo[4.2.1.02,5]nonene

Daştan, Arif; Uzundumlu, Eren; Balcı, Metin; Fabris, Fabrizio; Lucchi, Ottorino De

doi:10.1002/ejoc.200300478

Cited by 18 publications

(5 citation statements)

References 26 publications

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“…This nonhygroscopic and stable reagent was known to afford excellent yields of homo- and heterocoupling products from vinylic or arylic halides and stannanes . CuTC promoted the cyclotrimerization of bromostannanes under very mild conditions, affording BCTs, which could not be obtained with the previous methodologies . Very importantly, CuTC furnished enantiopure functionalized benzocyclotrimers with almost complete syn -diasteroselectivity (Scheme ) …”

Section: Benzocyclotrimers: Synthesismentioning

confidence: 99%

Benzocyclotrimers: From the Mills−Nixon Effect to Gas Hosting

et al. 2011

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The formal annulation of three bicylic olefins yields a class of molecules termed benzocyclotrimers (BCTs), which have unusual electronic properties. The bonds in the central aromatic ring, for example, alternate in length: rather than resembling a substituted benzene, a BCT instead evokes comparison to a cyclohexatriene. Forty years have passed since the synthesis of heptiptycene, the first BCT, was reported. In the interim, many methods have been developed for preparing tris-bicycloannulated benzenes. More than thirty different BCTs have so far been reported, with a variety of morphological features and properties. Over the same period, yields have increased from just a few percent to almost quantitative conversion. This improvement in synthetic access has expanded interest beyond the original theoretical considerations (bond-length fixation in aromatics) to functional applications (supramolecular scaffolds). In this Account, we describe the evolution of synthetic approaches to BCTs and their derivatives, as well as the applications that are now being explored for these compounds. Early syntheses of BCTs involved chloroolefins treated with butyl lithium. A strained alkyne intermediate was postulated early on, and was indeed trapped in 1981. Subsequent efforts have focused on improving chemoselectivity by mitigating the drastic conditions required for the generation of the alkyne intermediate. Our introduction of Cu(I) to induce lithium-copper exchange was successful in this regard. Further improvement resulted from the use of bicylic bromo(trimethylstannyl)olefins. In an effort to avoid the toxicity of the tin reagents, the Heck reaction and Pd catalysis have been pursued for cyclotrimerizing bicylic bromo- and iodoolefins. Depending on the symmetry of the starting bicylic olefin, two diastereomers can be obtained in the preparation of a BCT: a syn compound with C(3) symmetry and an anti compound with C(s) symmetry. Studying the diastereomeric outcome in a variety of synthetic approaches has yielded valuable insight into the cyclotrimerization reaction. Moreover, highly symmetric compounds, such as a D(3)-symmetric trindane and C(3v)-symmetric sumanene, have been prepared as BCT derivatives. The structure of BCTs offers a versatile three-dimensional scaffold for studying molecular recognition. Like calixarenes, BCTs form complexes with a variety of guest molecules. Recent developments include the trapping of gases in a hydrogen-bonded dimer and the encapsulation of larger molecules within a covalently linked condensation derivative. Future innovations in this fertile research area will likely include highly functionalized curved aromatics, receptors, and sensors.

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Section: Benzocyclotrimers: Synthesismentioning

confidence: 99%

Benzocyclotrimers: From the Mills−Nixon Effect to Gas Hosting

et al. 2011

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“…In the continuation of the designed work, the aim was to investigate different methods for obtaining new and innovative conduritol derivatives. For this purpose, the double bond of compound 10 was brominated in DCM at room temperature to produce tribromide 20 then it was converted to cyclohexene di‐bromide 21 [23] by elimination reaction using DBU in absolute benzene [24] . After the isolation, purification and configuration assignment for 21 , the bromine atoms were replaced with phenyl groups to design new conduritol derivatives.…”

Section: Resultsmentioning

confidence: 99%

“…After successful bromination of compound 14, was produced compound 27 quantitatively. Without isolation and purification, compound 27 was eliminated, as in compound 21, [23,24] afforded compound 28 as sole product with 78 % yield. After acquiring dibromo-alkene 28, the bromine atoms were selectively converted to phenyl groups [20] as for compound 22, smoothly producing compound 29 (Scheme 7).…”

Section: Chemistrymentioning

confidence: 99%

Versatile Synthesis of rac‐ and meso‐Hydroxymethyl Cyclohexenoids Containing Phenyl Groups: α‐/β‐Glucosidase Activities, Inhibition Kinetics and Molecular Docking Studies

et al. 2022

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The effective strategy has been developed to synthesize a series of monophenyl and diphenyl carbasugar analogues, from the cycloadduct reaction of furan and maleic anhydride, containing halogen groups based on the conduritol scaffold. The strategy mainly consists of reduction, esterification, bromination, formation of new double bond and replacement of bromine with phenyl by Suzuki coupling reaction. New phenyl-substituted carbasugars were obtained by cleavage of the oxo bridge and subsequent hydrolysis of the esters. The structures of the target compounds were defined using different chemical methods. In vitro inhibitory activity studies, kinetic and molecular docking studies were performed against α-, β-glucosidase enzymes for the final compounds.

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“…The mixture of diastereomers was dehydrobrominated with potassium tert-butoxide in THF, 26 to afford the alkenyldibromide 8 in good yield (93%) (Scheme 1). The key reagent 9 for the cyclotrimerization was obtained either by proton abstraction of halide 6 with lithium diisopropylamide (LDA) 11,13,[27][28][29][30][31][32][33] or by removal of one of the bromine atoms of the dibromide 8 with nbutyl lithium 30,31,34,35 followed by a trans-metalation reaction with trimethyltin chloride in 96% yield in both cases. The high chemoselectivity of removal of the bromine atom in 8 was surprisingly: indeed, the bromine atoms attached to the aromatic ring remained completely unaffected.…”

Section: Resultsmentioning

confidence: 99%

Highly diastereoselective synthesis of a novel functionalized benzocyclotrimer

Erdoğan¹,

Eşsiz²,

Fabris³

et al. 2018

Arkivoc

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The high yielding synthesis of a novel benzocyclotrimer is herein presented. The syn-diastereomer is obtained as major product, presumably in virtue of the presence of an oxa-bridge of the bicylic components. The three oxa-bridges can be used for further functionalization, as well as the six bromine atoms of the three aromatic rings, as demonstrated in the aromatization of a mixture of anti-1 and syn-1 (3:7) leading to trinaphthylene.

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An Investigation on the Synthesis of New Molecular Architectures from the Cyclotrimerisation of exo‐ and endo‐Benzotricyclo[4.2.1.0^2,5]nonene

Cited by 18 publications

References 26 publications

Benzocyclotrimers: From the Mills−Nixon Effect to Gas Hosting

Benzocyclotrimers: From the Mills−Nixon Effect to Gas Hosting

Versatile Synthesis of rac‐ and meso‐Hydroxymethyl Cyclohexenoids Containing Phenyl Groups: α‐/β‐Glucosidase Activities, Inhibition Kinetics and Molecular Docking Studies

Highly diastereoselective synthesis of a novel functionalized benzocyclotrimer

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