New Biphenylenophanes and Biphenylophanes – 1,8‐Dimethylbiphenylene by Continuous Vacuum Pyrolysis

Laufenberg, Susanne; Feuerbacher, Nina; Pischel, Ivo; Börsch, Oliver; Nieger, Martin; Vögtle, Fritz

doi:10.1002/jlac.199719970915

Cited by 14 publications

(15 citation statements)

References 48 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Analogous syn-[2.2]biphenylenophane (37), in which an additional 2,2 0 -linkage is introduced to 36, was enantiomerically enriched under the same HPLC conditions. Upon CD spectral examination, similar Cotton effect patterns were observed in the 180-300 nm region [49]. …”

Section: Other Cyclophanessupporting

confidence: 57%

Recent Theoretical and Experimental Advances in the Electronic Circular Dichroisms of Planar Chiral Cyclophanes

Mori

Inoue

2010

Electronic and Magnetic Properties of Chiral Molecules and Supramolecular Architectures

View full text Add to dashboard Cite

The chiroptical properties, such as electronic and vibrational circular dichroism and optical rotation, of planar chiral cyclophanes have attracted much attention in recent years. Although the chemistry of cyclophanes has been extensively explored for more than 60 years, the studies on chiral cyclophanes are rather limited. Experimentally, the use of chiral stationary phases in HPLC becomes more popular and facilitates the enantiomer separation of chiral cyclophanes of interest. Almost all chiral cyclophanes can be readily separated, in analytical and preparative scales, most typically on a Daicel OD type column, which is based on cellulose tris(3,5-dimethylphenylcarbamate). The CD spectra of chiral cyclophanes are unique in their fairly large, significantly coupled Cotton effects observed in all the 1 B b , 1 L a , and 1 L b band regions. Theoretically, the time-dependent density functional theory, or TD-DFT, method becomes a cost-efficient, yet accurate, theoretical method to reproduce the electronic circular dichroisms and the absorption spectra of a variety of cyclophanes. The direct comparison of the experimental CD spectra with the theoretical ones readily leads to the unambiguous assignment of the absolute configuration of cyclophanes. In addition, the analysis of configuration interaction and molecular orbitals allows detailed interpretation of the electronic transitions and Cotton effects in the UV and CD spectra. Through the study of the CD spectra of chiral cyclophanes as model systems, the effects of intra-and intermolecular interactions on the chiroptical properties of molecules can be explored, and the results thus obtained are valuable in comprehensively elucidating the structure-chiroptical property relationship. In this review the recent progress in experimental and theoretical investigations of the electronic CD spectra of chiral cyclophanes is discussed.

show abstract

Section: Other Cyclophanessupporting

confidence: 57%

Recent Theoretical and Experimental Advances in the Electronic Circular Dichroisms of Planar Chiral Cyclophanes

Mori

Inoue

2010

Electronic and Magnetic Properties of Chiral Molecules and Supramolecular Architectures

View full text Add to dashboard Cite

show abstract

“…-IR (KBr): ν/cm -1 = 1 100 -1 330 (SO 2 ). (8) was placed at the bottom of a quartz tube (diameter 10 mm, length 500 mm). Tube was heated to 610 °C in vacuo (2×10 -4 torr) using the ring oven sulfone pyrolysis apparatus (Fig.…”

Section: 10-dithia[332]mpp-cyclophane (7)mentioning

confidence: 99%

“…A very brief structural proof (MS and NMR) for the [2.2.2]m,m,mcyclophane (tri-m-xylylene) as a side product of a Wurtz reaction was given by Jenny and Burri in 1966 [30]. In this paper we report the HD-2SO 2 [4,5,8,23].…”

mentioning

confidence: 90%

“…The combination of these two methods into HD-SO 2 -method (High-dilution cyclisation reaction of a bis-bromide and a bis-thiol to a cyclic n membered bis-sulphide followed by oxidation to the corresponding cyclic bis-sulfone and subsequent extrusion of 2 moles of SO 2 under vacuum and elevated temperatures leading to a (n-2) membered cyclophane), has had a major impact on the synthesis of strained cyclophanes as shown by the pioneering work of Vögtle over more than three decades [6]. Professor Vögtle's impact on the HD-SO 2 -method has also materialised as inventions of specific equipment designed particularly for this type of synthetic work, these include high dilution apparatus [7] (Fig 1.) and ring oven apparatus for the vacuum pyrolysis of sulfones [8] (Fig. 2.).…”

mentioning

confidence: 99%

“…The yields for the oxidation reactions were 33, 64 and 85% for 8, 9 and 10, respectively. The disulfones 9 and 10 were pyrolysed to the desired cyclophanes, namely [2.2.2]m,m,p-cyclophane (12) and [2.2.2]m,p,p-cyclophane (13) by using the ring oven pyrolysis apparatus [8,Fig 1b. ] at 600 °C and 1 -2× 10 -5 torr.…”

mentioning

confidence: 99%

See 2 more Smart Citations

Concave π-prismand hydrocarbon [2.2.2]cyclophanes and their crystalline Ag-triflate complexes

et al. 1999

View full text Add to dashboard Cite

237High dilution principle and its use as a synthetic tool has been widely recognised and was reviewed by Vögtle in 1991 [1]. Particularly cyclophane [2] and supramolecular chemistry [3] have gained a lot owing to the use of HD principle, in spite of the rather poor yields associated with its use. Another very useful synthetic tool, namely sulfone pyrolysis developed in late 1960's, has been of tremendous help in preparing highly strained (macro)cyclic compounds. Sulfone pyrolysis and its use as a synthesis method has been twice reviewed by Vögtle, first in 1979 [4] and then in 1991 [5]. The combination of these two methods into HD-SO 2 -method (High-dilution cyclisation reaction of a bis-bromide and a bis-thiol to a cyclic n membered bis-sulphide followed by oxidation to the corresponding cyclic bis-sulfone and subsequent extrusion of 2 moles of SO 2 under vacuum and elevated temperatures leading to a (n-2) membered cyclophane), has had a major impact on the synthesis of strained cyclophanes as shown by the pioneering work of Vögtle over more than three decades [6]. Professor Vögtle's impact on the HD-SO 2 -method has also materialised as inventions of specific equipment designed particularly for this type of synthetic work, these include high dilution apparatus [7] (Fig 1.) and ring oven apparatus for the vacuum pyrolysis of sulfones [8] (Fig. 2.).During our ten year collaboration with Professor Vögtle the use of the HD-and HD-SO 2 -method has successfully been employed to the synthesis of helically chiral cyclophanes, bicyclic compounds, extremely strained hydrocarbons, thiaand pyridinophanes and most recently concave hydrocarbon cyclophanes [9 -26].In p,p,p-cyclophane and claimed that it was the first member of a new class of compounds. Owing to its structure and complexation properties they proposed the name π-prismand for such hydrocarbon cyclophanes [28]. Further studies revealed that in the π-prismand-Ag + complex the silver ion is bonded not to the centre of the benzene ring but to edge of the cavity owing to a specific interaction with one carbon-carbon double bond in each phenyl moiety [29] ,m,m-, m,m,p-and m,p,p-cyclophane, the latter two being previously unknown. The complexation with silver triflate was studied for the m,m,p-and m,p,p-cyclophanes.

show abstract

Structure/Chiroptics Relationships of Planar Chiral and Helical Molecules

Grimme¹,

et al. 1998

Self Cite

View full text Add to dashboard Cite

New Biphenylenophanes and Biphenylophanes – 1,8‐Dimethylbiphenylene by Continuous Vacuum Pyrolysis

Cited by 14 publications

References 48 publications

Recent Theoretical and Experimental Advances in the Electronic Circular Dichroisms of Planar Chiral Cyclophanes

Recent Theoretical and Experimental Advances in the Electronic Circular Dichroisms of Planar Chiral Cyclophanes

Concave π-prismand hydrocarbon [2.2.2]cyclophanes and their crystalline Ag-triflate complexes

Structure/Chiroptics Relationships of Planar Chiral and Helical Molecules

Contact Info

Product

Resources

About