Synthetic transformation of 1,3-diarylisobenzofuran-DMAD adducts: a facile preparation of tri-substituted α-naphthols

Karunakaran, Jayachandran; Nandakumar, Meganathan; Kumar, Naresh; Mohanakrishnan, Arasambattu K.

doi:10.1039/c6ob00628k

Cited by 11 publications

(8 citation statements)

References 47 publications

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“…We used 10 to generate in situ the parent benzyne for the Diels–Alder reactions with the two 2,5-diphenylfuran units in syn - 9 and anti - 9 . Treatment of a mixture of syn - 9 and anti - 9 with an excess of 10 in refluxing 1,2-dichloroethane was successful in forming the two 1,4-epoxynaphthalene units in 11 (Scheme ), which underwent 1,2-aryl migration with ring opening of the 1,4-epoxy moieties in attempts to isolate by silica gel column chromatography. Fortunately, upon exposure of the crude reaction products to Fe 2 (CO) 9 in refluxing benzene for reductive deoxygenation, 11 was transformed smoothly to produce a mixture of syn - 12 and anti - 12 (isomer ratio = 2:1) in 92% combined yield over two steps.…”

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confidence: 99%

Synthesis and Characterization of Functionalized [12]Cycloparaphenylenes Containing Four Alternating Biphenyl and Naphthyl Units

et al. 2017

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Functionalized [12]cycloparaphenylenes ([12]CPPs) containing four alternating biphenyl and naphthyl units were synthesized. A macrocyclic furan-containing CPP precursor was used for the Diels-Alder reaction with the parent benzyne or 3,6-dimethoxybenzyne to form the corresponding macrocyclic carbon frameworks. The subsequent reductive deoxygenation of the Diels-Alder adducts with Fe(CO) followed by oxidative aromatization with 2,3-dichloro-5,6-dicyano-1,4-benzoquinone produced the functionalized [12]CPPs. The effect of macrocyclic ring size on the reaction rate of oxidative aromatization was investigated.

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confidence: 99%

Synthesis and Characterization of Functionalized [12]Cycloparaphenylenes Containing Four Alternating Biphenyl and Naphthyl Units

et al. 2017

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“…In a similar manner to [ 15 ], 1,3-diphenylisobenozfuran ( 2 , 0.10 g, 0.37 mmol), 5 mL CH 2 Cl 2 and dimethyl acetylenedicarboxylate (DMAD, 0.116 g, 0.814 mmol) were added to a round bottom flask. The reaction mixture was stirred at room temperature for 2 hours.…”

Section: Methodsmentioning

confidence: 99%

Kinetically stabilized 1,3-diarylisobenzofurans and the possibility of preparing large, persistent isoacenofurans with unusually small HOMO–LUMO gaps

Liu,

Miller

2024

Beilstein J. Org. Chem.

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DFT calculations demonstrate that an isoacenofuran of any size possesses a smaller HOMO–LUMO gap than the corresponding acene bearing an isoelectronic π-system (i.e., the same total number of rings). Isoacenofurans show limited stability due in part to the highly reactive 1,3-carbons of the furan ring. Both 1,3-dimesitylisobenzofuran and 1,3-di(2’,4’,6’-triethylphenyl)isobenzofuran, each bearing sterically congesting ortho-alkyl groups on their phenyl substituents, have been synthesized and shown to adopt non-planar conformations with the ortho-alkyl groups located above and below the most reactive 1,3-carbons of the furan ring. These bulky substituents provide a strong measure of kinetic stabilization. Thus, 1,3-dimesitylisobenzofuran and 1,3-di(2’,4’,6’-triethylphenyl)isobenzofuran are significantly less reactive than 1,3-diphenylisobenzofuran toward the strong dienophiles DMAD and acrylonitrile. The insights gained here suggest that the synthesis of large, persistent, kinetically stabilized isoacenofurans with unusually small HOMO–LUMO gaps is achievable. As such, these molecules deserve increased attention as potential p-type organic semiconductors.

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“…Acenaphthylene (≈ 75 %) was purchased from Sigma–Aldrich and used as received. Required benzo[ c ]furans 1a – 1z , 1aa – 1am , 4a , 4b , 6a , 6b , 8a , and 8b were prepared by using our published procedures , …”

Section: Methodsmentioning

confidence: 99%

“…We have also explored the synthetic utility of 1,3‐disubstituted benzo[ c ]furans to assemble a wide variety of π‐conjugated heterocycles and carbocycles . In consideration of the enormous application potential, a systematic study of Diels–Alder reactions of symmetrical/unsymmetrical 1,3‐diaryl/heteroaryl benzo[ c ]furans with acenaphthylene 2 was planned to access diversely substituted benzo[ k ]fluoranthene derivatives (Scheme ).…”

Section: Introductionmentioning

confidence: 99%

Synthesis of Benzo[k]fluoranthene Derivatives through Diels–Alder Reaction of 1,3‐Diarylbenzo[c]furans

Karunakaran

Mohanakrishnan

2017

Eur J Org Chem

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Diels–Alder reaction of symmetrical/unsymmetrical benzo[c]furans with acenaphthylene in xylenes at reflux temperatures followed by p‐toluenesulfonic acid‐mediated epoxide cleavage and dehydration furnished diaryl/heteroaryl‐substituted benzo[k]fluoranthenes. This strategy could be successfully applied to the synthesis of dimeric and trimeric benzo[k]fluoranthenes. Functionalization of representative benzo[k]fluoranthene derivatives was also performed. UV/Visible, emission and electrochemical properties of representative fluoranthene derivatives are also reported.

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Synthetic transformation of 1,3-diarylisobenzofuran-DMAD adducts: a facile preparation of tri-substituted α-naphthols

Abstract: 1,3-Diarylisobenzofuran-DMAD adducts upon reaction with BF3·OEt2 in DCM at room temperature underwent a regiospecific 1,2-aryl migration followed by the Krapcho decarboxylation to give tri-substituted α-naphthols in good yields.

Cited by 11 publications

References 47 publications

Synthesis and Characterization of Functionalized [12]Cycloparaphenylenes Containing Four Alternating Biphenyl and Naphthyl Units

Synthesis and Characterization of Functionalized [12]Cycloparaphenylenes Containing Four Alternating Biphenyl and Naphthyl Units

Kinetically stabilized 1,3-diarylisobenzofurans and the possibility of preparing large, persistent isoacenofurans with unusually small HOMO–LUMO gaps

Synthesis of Benzo[k]fluoranthene Derivatives through Diels–Alder Reaction of 1,3‐Diarylbenzo[c]furans

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