Supramolecular Catalysis at Work:  Diastereoselective Synthesis of a Molecular Bowl with Dynamic Inner Space

Yan, Zhiqing; McCracken, Troy M.; Xia, Shijing; Maslak, Veselin; Gallucci, Judith C.; Hadad, Christopher M.; Badjić, Jovica D.

doi:10.1021/jo701538g

Cited by 31 publications

(28 citation statements)

References 71 publications

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“…5A). 46,47 In particular, De Lucchi and co-workers have developed 48 a variety of useful cyclotrimerization protocols. The reaction gives a mixture of syn/anti diastereomeric products (Fig.…”

Section: Design and Preparationmentioning

confidence: 99%

Gated molecular baskets

et al. 2015

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In this review, we describe the construction of gated molecular baskets, discuss their mechanism of action in regulating the exchange of guests and illustrate the potential of these concave hosts to act as catalysts for controlling chemical reactions. Importantly, a number of computational and experimental studies have suggested that gated baskets ought to unfold their gates at the rim for permitting the passage of guests to/from their inner space. These dynamic hosts are therefore offered as useful models for investigating the process of gating in artificial systems. Furthermore, gated baskets should permit examining the benefit of controlling the rate by which reactants access a gated catalyst for promoting chemical reactions occurring in its confined space.

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Section: Design and Preparationmentioning

confidence: 99%

Gated molecular baskets

et al. 2015

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“…The almost complete anti-diastereoselectivity of this reaction was reversed using a suitable metal as templating agent. 19 2.3. BCT from Halo Bicyclic Olefins.…”

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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“…1 This behaviour has been previously observed when a ligating group is present in the monomer. 37,38,11,32 It is likely that the oxa-bridge in the dihydronaphthalene is responsible for the high reverse selectivity, by means of coordination with copper. The separation of the two isomers was easily accomplished by chromatography on neutral alumina and the major syn-1 isomer was available for further functionalization and supramolecular studies.…”

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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Supramolecular Catalysis at Work: Diastereoselective Synthesis of a Molecular Bowl with Dynamic Inner Space

Cited by 31 publications

References 71 publications

Gated molecular baskets

Gated molecular baskets

Benzocyclotrimers: From the Mills−Nixon Effect to Gas Hosting

Highly diastereoselective synthesis of a novel functionalized benzocyclotrimer

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