Synthesis of <i>p</i>-Quinquephenyl from <i>E,E</i>-1,4-Bis(4-bromophenyl)-1,3-butadiene

Davis, Matthew C.; Groshens, Thomas J.

doi:10.1080/00397910903533991

Cited by 13 publications

(19 citation statements)

References 26 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Jørgensen’s asymmetric organocatalytic Michael addition of malonates to α,β-unsaturated aldehydes was applied toward the synthesis of 4-bromoparoxetine ( 13 , Figure C). 4-Bromocinnamaldehyde ( 7 ) was subjected to a conjugate addition of dibenzyl malonate using 10 mol % of the commercially available l -proline-derived ( S )-Catalyst* [( S )-2-[bis(3,5-bistrifluoromethylphenyl) trimethylsilanyloxymethyl]-pyrrolidine] to provide the β-malonylaldehyde 8 in 84% yield and 90% enantiomeric excess (ee) . Reductive amination with commercially available 4-methoxybenzylamine and in situ cyclization gave lactam 9 .…”

Section: Resultsmentioning

confidence: 99%

A Novel Bromine-Containing Paroxetine Analogue Provides Mechanistic Clues for Binding Ambiguity at the Central Primary Binding Site of the Serotonin Transporter

Slack

Abramyan

Tang

et al. 2019

ACS Chem. Neurosci.

View full text Add to dashboard Cite

The serotonin transporter (SERT) is the primary target for the selective serotonin reuptake inhibitors (SSRIs). However, the structural basis for the extraordinarily high binding affinity of the widely prescribed SSRI, paroxetine, to human SERT (hSERT) has not yet been fully elucidated. Our previous findings unveiled a plausible ambiguity in paroxetine's binding orientations that may constitute an integral component of this SSRI's high affinity for hSERT. Herein, we investigate factors contributing to paroxetine's high affinity by modifying both the ligand and the protein. We generated a series of bromine (Br)-containing derivatives and found that the one in which the 4-F of paroxetine had been replaced with the chemically similar but more electron-rich Br atom (13) had the highest affinity. By comparatively characterizing the binding of paroxetine and 13 to both wild type (WT) and a construct harboring a paroxetine-sensitive mutation in the binding cavity, we identified a mechanistic determinant responsible for the pose ambiguity of paroxetine, which can guide future drug design.

show abstract

Section: Resultsmentioning

confidence: 99%

A Novel Bromine-Containing Paroxetine Analogue Provides Mechanistic Clues for Binding Ambiguity at the Central Primary Binding Site of the Serotonin Transporter

Slack

Abramyan

Tang

et al. 2019

ACS Chem. Neurosci.

View full text Add to dashboard Cite

show abstract

“…3 One of the current frontiers of investigation in this area involves preparation of substituted and functionalized CPPs for connection with a nanotube-like arrangement. The 1,4benzene-and 1,5-naphthalene-bridged [8]CPP dimers were synthesized, 4 and a directly connected [10]CPP dimer was constructed. 5 We now report our development of synthetic pathways leading to fused macrocycles bearing two partially hydrogenated CPP units with armchair nanotube-like connections.…”

Section: ■ Introductionmentioning

confidence: 74%

“…All air- and moisture-sensitive reactions were conducted in oven-dried (120 °C) glassware under a nitrogen atmosphere. ( E , E )-1,4-Bis(4-bromophenyl)-1,3-butadiene ( 1 ) and 1,4-bis[4-(trimethylsilyl)phenyl]-1,3-butadiyne were prepared according to the reported procedures. Boron trifluoride diethyl etherate (BF 3 ·OEt 2 ), 1,4-benzoquinone ( 2 ), silver(I) oxide (Ag 2 O), dimethyl sulfate, bis(1,5-cyclooctadiene)nickel [Ni(cod) 2 ], 2,2′-bipyridyl (bpy), aluminum chloride (AlCl 3 ), iodine chloride (ICl), n -butyllithium in hexanes (1.6 M), triethylsilane, [1,1′-bis(diphenylphosphino)ferrocene]dichloropalladium(II) [Pd(dppf)Cl 2 ], palladium(II) acetate [Pd(OAc) 2 ], 1,1′-bis(diphenylphosphino)ferrocene (dppf), copper(II) sulfate (CuSO 4 ), and 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ) were purchased from chemical suppliers and were used as received.…”

Section: Methodsmentioning

confidence: 99%

Synthesis of Partially Hydrogenated Cycloparaphenylenes with Bent and Fused Structures Bearing Armchair Carbon Nanotube-like Connections

Huang

Thakellapalli

et al. 2017

J. Org. Chem.

View full text Add to dashboard Cite

The Diels-Alder reactions between 2 equiv of (E,E)-1,4-bis(4-bromophenyl)-1,3-butadiene and 1,4-benzoquinone led to the formation of a key intermediate with all four 4-bromophenyl substituents cis to one another. The subsequent nickel-mediated homocoupling reactions then produced partially hydrogenated cycloparaphenylenes, including a molecule bearing two units of tetrahydro[6]cycloparaphenylene (4H[6]CPP) fused together through two 1,4-dimethoxybenzene units in an armchair (6,6)carbon nanotube-like connection. Similarly, two 6H[9]CPPs were connected through three 1,4-dimethoxybenzene units in an armchair (9,9)carbon nanotube-like arrangement. A bent 8H[12]CPP and a bent 12H[18]CPP, which were fused intramolecularly with two and three 1,4-dimethoxybenzene units, respectively, to create the bent structures, were likewise synthesized. A molecule containing a bent 8H[12]CPP fused to a 4H[6]CPP was likewise constructed. The structures of these partially hydrogenated CPPs were established by X-ray structure analysis, NMR spectroscopy, and additional independent synthetic pathways.

show abstract

“…vations. 19,20 Table 5 reports the total electronic, Gibbs free energies, and torsional angles of oligo-p-phenylenes (2-6) calculated by B3LYP/6-311G(d,p). The relative energies between the twisted and planar conformations of the oligomers show that the longer planar oligomer gives higher instability by additional steric hindrances between the adjacent phenyl groups of the planar conformer.…”

Section: Bcmentioning

confidence: 99%

Calculated and Experimental UV and IR Spectra of Oligo-para-phenylenes

Park¹,

Lee²,

Yoon³

et al. 2014

Bulletin of the Korean Chemical Society

View full text Add to dashboard Cite

The quantum mechanical properties of a series of oligo-para-phenylenes (2-11) were characterized using DFT B3LYP/6-311G(d,p) calculations. The global minimum among the various torsional conformers of an oligo-pphenylene is calculated to be a twist conformation. A less stable planar conformation, in which all the dihedral angles in oligo-p-phenylene are restricted to be planar, has also been calculated. The total electronic energies, normal vibrational modes, Gibbs free energies, and HOMOs and LUMOs of the two different conformations (twisted and planar) of the oligo-p-phenylenes were analyzed. The energy differences between the HOMOs and LUMOs of the substrates are in accord with the maximum absorption peaks of the experimental UV spectra of 2-6. The calculated normal vibrational modes of 2-6 were comparable with their experimental IR spectra.

show abstract

Synthesis of p-Quinquephenyl from E,E-1,4-Bis(4-bromophenyl)-1,3-butadiene

Cited by 13 publications

References 26 publications

A Novel Bromine-Containing Paroxetine Analogue Provides Mechanistic Clues for Binding Ambiguity at the Central Primary Binding Site of the Serotonin Transporter

A Novel Bromine-Containing Paroxetine Analogue Provides Mechanistic Clues for Binding Ambiguity at the Central Primary Binding Site of the Serotonin Transporter

Synthesis of Partially Hydrogenated Cycloparaphenylenes with Bent and Fused Structures Bearing Armchair Carbon Nanotube-like Connections

Calculated and Experimental UV and IR Spectra of Oligo-para-phenylenes

Contact Info

Product

Resources

About