Benzotrifuranone: Synthesis, Structure, and Access to Polycyclic Heteroaromatics

Li, Yan; Lampkins, Andrew J.; Baker, Matthew B.; Sumpter, Bobby G.; Huang, Jingsong; Abboud, Khalil A.; Castellano, Ronald K.

doi:10.1021/ol901631n

Cited by 26 publications

(18 citation statements)

References 48 publications

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“…Subsequent demethylation using BBr 3 at low temperature provided the phloroglucinol targets 4a and 4b in excellent yield. To generate a small library of model compounds 5 , we have capitalized on the versatile aminolysis chemistry of benzotrifuranone (BTF) 8 5e–5g (Table 5). Shown is the treatment of BTF with various aliphatic ( a – e ) and one aromatic ( f ) amines; the former include primary ( a ), branched/chiral ( b ), secondary acyclic ( c ), and secondary cyclic ( d and e ) derivatives that subtly vary the H‐bond accepting ability of the amide carbonyl.…”

Section: Resultsmentioning

confidence: 99%

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Seven‐Membered Intramolecular Hydrogen Bonding of Phenols: Database Analysis and Phloroglucinol Model Compounds

Castellano

Homan

et al. 2012

Eur J Org Chem

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Seven‐membered intramolecular hydrogen bonding (7MHB) arrangements involving phenolic hydroxyl group donors have been investigated through Cambridge Structural Database (CSD) and literature mining, and by the characterization of model compounds. The CSD reveals the numerous H‐bond accepting functional groups that can participate in 7MHB when they are proximal to a phenolic OH, including alcohols, amides, amines, ethers, N‐containing heterocycles, ketones, N‐oxides, phosphates, and phosphane oxides. The HB contacts are defined by Ophenol···N and Ophenol···O distances of ca. 2.7 Å, and two dihedral angles that fall within the range of typical peptide γ‐turns. Two of the identified 7MHB motifs have been readily mapped onto the phloroglucinol (1,3,5‐trihydroxybenzene) scaffold to provide eight model compounds; intramolecular hydrogen bonding involving all three hydroxyl groups is shown to persist in solution and the solid state for the compounds. Intramolecular 7MHB enforces nonplanar conformations that should be useful when designing molecular hosts and catalysts.

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Section: Resultsmentioning

confidence: 99%

“…CI‐MS spectra were recorded with a Thermo Scientific Trace GC DSQ (single quadrupole) spectrometer. Compounds 6 5a and 8 5e–5g were prepared as described in the literature.…”

Section: Methodsmentioning

confidence: 99%

Seven‐Membered Intramolecular Hydrogen Bonding of Phenols: Database Analysis and Phloroglucinol Model Compounds

Castellano

Homan

et al. 2012

Eur J Org Chem

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“…BTF (3) was synthesised on a multi-gram scale according to recently published methods (18). As shown in Table 1, a variety of electron-rich and -deficient anilines could be used to open the lactone rings of 3, providing rapid access to phloroglucinol substrates for cyclisation into AATs.…”

Section: Resultsmentioning

confidence: 99%

“…The nature of the 'communication' is presumably largely inductive, but could more subtly involve ring strain and p-conjugation effects that would accompany trace amounts of enol or enolate forms (18). Although the physicochemical details are still very much under investigation, the hypothesis seems plausible given the preliminary results using 3 and aniline ( Figure 3).…”

Section: Synthesis Of C S -Symmetric Aatsmentioning

confidence: 98%

“…Two relatively simple aryl amide AATs have been prepared in this way (1a and 1b, Table 1), (12) but the demanding and late-stage deprotection step has limited access to a structurally diverse family of compounds. A straightforward solution is presented here, made possible by the recent development of a phloroglucinol-derived trilactone, benzotrifuranone (BTF) 3 ( Figure 2) (18).…”

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Rapid access to C ₃- and C _s-symmetric AAT organogelators via ring opening of a common benzotrifuranone precursor

Baker

Yuan

Marth

et al. 2010

Supramolecular Chemistry

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2010) Rapid access to C 3 -and C s -symmetric AAT organogelators via ring opening of a common benzotrifuranone precursor, Supramolecular Chemistry,[789][790][791][792][793][794][795][796][797][798][799][800][801][802] Presented is a rapid and general approach to functionalised 1-aza-adamantanetrione (AAT) donor-s-acceptor molecules from a phloroglucinol-derived trilactone, benzotrifuranone (BTF). Ten C 3 -symmetric AATs bearing diverse aryl amide substituents are accessed in two synthetic steps: (1) the exhaustive ring opening of BTF with aromatic amine nucleophiles (performed in up to 91% yield) and (2) cyclisation with hexamethylenetetramine (performed in up to 75% yield). Additionally, stepwise ring opening of BTF allows synthesis of phloroglucinol intermediates with two unique aryl amide substituents and ultimately C s -symmetric AATs. Of the novel AATs prepared, three (including the C s -symmetric hybrid) are effective gelators of chlorinated solvents (critical gelation concentration (CGC) ¼ 0.2 -0.4 wt%) and one, with naphthyl substituents, forms translucent gels from aromatic solvents (CGC , 0.3 wt%). The combination of AATs with moderately electron-poor and electron-rich aromatic substituents results in functional complementarity and gelation at concentrations below what is required for the individual components. Electron microscopy of the gel morphologies shows high aspect ratio fibres underlying the gel network superstructures in most cases. Polarised optical microscopy has allowed imaging of representative native organogel phases, and reveals striking morphology differences between gels that also share different optical and/or thermal stability properties.

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Enantioselective Base‐Free Electrophilic Amination of Benzofuran‐2(3H)‐ones: Catalysis by Binol‐Derived P‐Spiro Quaternary Phosphonium Salts

et al. 2011

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A spiroing reactivity: A series of novel binol‐derived P‐spiro quaternary phosphonium salts were designed, prepared, and used for the first highly enantioselective amination of benzofuranones (see scheme; binol=1,1′‐2‐binaphthol, Bn=benzyl). An unprecedented mechanism involving the π–π interactions between the substrate and the catalyst was proposed as the primary binding mode on the basis of molecular modelling and DFT calculations.

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Benzotrifuranone: Synthesis, Structure, and Access to Polycyclic Heteroaromatics

Cited by 26 publications

References 48 publications

Seven‐Membered Intramolecular Hydrogen Bonding of Phenols: Database Analysis and Phloroglucinol Model Compounds

Seven‐Membered Intramolecular Hydrogen Bonding of Phenols: Database Analysis and Phloroglucinol Model Compounds

Rapid access to C ₃- and C _s-symmetric AAT organogelators via ring opening of a common benzotrifuranone precursor

Enantioselective Base‐Free Electrophilic Amination of Benzofuran‐2(3H)‐ones: Catalysis by Binol‐Derived P‐Spiro Quaternary Phosphonium Salts

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Benzotrifuranone: Synthesis, Structure, and Access to Polycyclic Heteroaromatics

Cited by 26 publications

References 48 publications

Seven‐Membered Intramolecular Hydrogen Bonding of Phenols: Database Analysis and Phloroglucinol Model Compounds

Seven‐Membered Intramolecular Hydrogen Bonding of Phenols: Database Analysis and Phloroglucinol Model Compounds

Rapid access to C 3- and C s-symmetric AAT organogelators via ring opening of a common benzotrifuranone precursor

Enantioselective Base‐Free Electrophilic Amination of Benzofuran‐2(3H)‐ones: Catalysis by Binol‐Derived P‐Spiro Quaternary Phosphonium Salts

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Rapid access to C ₃- and C _s-symmetric AAT organogelators via ring opening of a common benzotrifuranone precursor