Ab initio study of the structures and dynamic stereochemistry of biaryls

Nori‐Shargh, Davood; Asadzadeh, S; Ghanizadeh, Fatemeh-Rozita; Deyhimi, Farzad; Amini, Mostafa M.; Jameh‐Bozorghi, Saeed

doi:10.1016/j.theochem.2004.11.022

Cited by 47 publications

(29 citation statements)

References 38 publications

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“…The rotational barrier was calculated to be at least 16.7 kcal/mol at 70 °C on the basis of the lack of coalescence of signals at this temperature. This lowest possible rotational barrier is significantly higher than that of 1-phenylnaphthalene, which was calculated by MM2' to be 12.4 kcal/mol [25–26]. Similarly, the 1 H NMR spectrum of 13b taken in CDCl 3 showed a clear AB system at δ 4.07 ( J = 13.8 Hz) and 4.04 ( J = 13.8 Hz), attributable to the methylene hydrogens on the carbon attached to the methoxy group.…”

Section: Resultsmentioning

confidence: 94%

Synthesis of 5-(2-methoxy-1-naphthyl)- and 5-[2-(methoxymethyl)-1-naphthyl]-11H-benzo[b]fluorene as 2,2'-disubstituted 1,1'-binaphthyls via benzannulated enyne–allenes

Wang¹,

Bailey²,

Petersen³

et al. 2011

Beilstein J. Org. Chem.

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Summary5-(2-Methoxy-1-naphthyl)- and 5-[2-(methoxymethyl)-1-naphthyl]-11H-benzo[b]fluorene were synthesized by treatment of the corresponding benzannulated enediynes with potassium tert-butoxide in refluxing toluene to give benzannulated enyne–allenes for the subsequent Schmittel cascade cyclization reactions. The structures of these two 5-(1-naphthyl)-11H-benzo[b]fluorenes could be regarded as 2,2'-disubstituted 1,1'-binaphthyls with the newly constructed benzofluorenyl group serving as a naphthyl moiety.

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Section: Resultsmentioning

confidence: 94%

Synthesis of 5-(2-methoxy-1-naphthyl)- and 5-[2-(methoxymethyl)-1-naphthyl]-11H-benzo[b]fluorene as 2,2'-disubstituted 1,1'-binaphthyls via benzannulated enyne–allenes

Wang¹,

Bailey²,

Petersen³

et al. 2011

Beilstein J. Org. Chem.

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“…To the best of our knowledge, despite the huge literature referring to BINAP applications based on Noyoris findings, [8,9] the enantiomerization barrier of BINAP 1 has not yet been explicitly reported. Nevertheless, such barriers have been calculated for less sterically congested related scaffolds, such as 1,1'-binaphthyl 3, [10,11] BINOL 2, [10,12,13] H-MOP 4, [14,15] and H-MIOP 5.[15] The complete enantiomerization pathway of BINAP has been computationally addressed and is reported for the first time hereafter, where it is first compared to the one of 1,1'-binaphthyl 3 taken as a reference. The relative configurational stability of selected related atropochiral molecules is then compared …”

mentioning

confidence: 99%

“…This is in agreement with previous DFT studies, in which the racemization barrier for the syn route was found 36.9 and 37.3 kJ mol À1 higher than for the anti route. [10,11] Note that semi-empirical MNDO, AM1, and PM3 calculations underestimate this difference. [17] The Gibbs free energy barrier of 101.5 kJ mol…”

mentioning

confidence: 99%

Enantiomerization Pathway and Atropochiral Stability of the BINAP Ligand: A Density Functional Theory Study

Garcı́a¹,

Lepetit²,

Canac³

et al. 2013

Chemistry An Asian Journal

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A theoretical study of the enantiomerization pathway of BINAP, the paradigm of atropochiral ligands in asymmetric organometallic catalysis, is reported. Density functional theory was used with the B3PW91 functional and the 6-31G(d,p) basis set. The calculation level was validated through the study of the syn and anti enantiomerization pathways of the 1,1′-binaphthyl reference for which the enantiomerization barrier was calculated to be in good agreement with experimental data. Calculations were then performed on BINAP itself using the same level of theory, and showed that its enantiomerization mechanism follows the syn route through a concerted, yet highly asynchronous, all-chiral process. The enantiomerization barrier was computed at 213 kJ mol(−1) and proved little sensitive to the functional or to the basis set used, with values always larger than 200 kJ mol(−1). The configurational stability of BINAP was finally characterized by a computed Oki’s racemization temperature of 491 °C.

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“…Unfortunately, many students are incapable to visualize in space and have difficulties in resolving the structure of the substance 1 . The possibilities to represent the structures either in two-or threedimensional representation are important to comprehend the bonds, isomerism, electronic configurations, and also the atom arrangements in particular molecules 7 . The modelling of chemical structures is essential to almost every chemical software package 4 .…”

Section: Model Structuresmentioning

confidence: 99%

Implementing and Operating Computer Graphics in the Contemporary Chemistry Education

Popovska¹

2017

Mediterr.J.Chem.,

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Technology plays a crucial role in modern teaching, providing both, educators and students fundamental theoretical insights as well as supporting the interpretation of experimental data. In the long term it gives students a clear stake in their learning processes. Advancing in education furthermore largely depends on providing valuable experiences and tools throughout digital and computer literacy. Here and after, the computer’s benefit makes no exception in the chemistry as a science. The major part of computer revolutionizing in the chemistry laboratory is with the use of images, diagrams, molecular models, graphs and specialized chemistry programs. In the sense of this, the teacher provides more interactive classes and numerous dynamic teaching methods along with advanced technology. All things considered, the aim of this article is to implement interactive teaching methods of chemistry subjects using chemistry computer graphics. A group of students (n = 30) at the age of 18–20 were testing using methods such as brainstorming, demonstration, working in pairs, and writing laboratory notebooks. The results showed that demonstration is the most acceptable interactive method (95%). This article is expected to be of high value to teachers and researchers of chemistry, implementing interactive methods, and operating computer graphics

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Ab initio study of the structures and dynamic stereochemistry of biaryls

Cited by 47 publications

References 38 publications

Synthesis of 5-(2-methoxy-1-naphthyl)- and 5-[2-(methoxymethyl)-1-naphthyl]-11H-benzo[b]fluorene as 2,2'-disubstituted 1,1'-binaphthyls via benzannulated enyne–allenes

Synthesis of 5-(2-methoxy-1-naphthyl)- and 5-[2-(methoxymethyl)-1-naphthyl]-11H-benzo[b]fluorene as 2,2'-disubstituted 1,1'-binaphthyls via benzannulated enyne–allenes

Enantiomerization Pathway and Atropochiral Stability of the BINAP Ligand: A Density Functional Theory Study

Implementing and Operating Computer Graphics in the Contemporary Chemistry Education

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