Synthesis of 7,7-dimethylnorbornadiene

Jefford, Charles W.; Wallace, Timothy W.; Can, Nguyen Thi Huong Can Nguyen Thi Huong; Rimbault, Christian G.

doi:10.1021/jo01319a005

Cited by 14 publications

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“…Turning now to (j19) and (j25), which are more closely related to artemisinin itself, the X-ray structure of (j25) has been determined previously [ 5 ] . Our overall results are again in good agreement, but when the two CH3 groups are replaced by the cyclopentane ring, the trioxane ring conformation is altered (Table VII).…”

Section: Comparison Ofartemisinin ( I ) (19) (25) (22) (23) and mentioning

confidence: 99%

Computational studies of the structures and properties of potential antimalarial compounds based on the 1,2,4-trioxane ring structure. I. Artemisinin-like molecules

Bérnardinelli

Jefford

Maric

et al. 1994

Int. J. Quantum Chem.

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Artemisinin and related molecules are potential antimalarials that contain the 1,2,4-lrioxane ring system. Several new derivatives have been synthesized and tested in Geneva, and this article presents the results of a systematic study of the structure of these molecules, both by the semiempirical PM3 method and using ab initio SCF methods. The results highlight the feasibility of full optimizations with 3-2 1G and 6-3 1G* basis sets for these large molecules. Molecular electrostatic potential (MEP) maps are evaluated and used in an attempt to identify the key features of the molecules that are necessary for their activity. There is good agreement between the PM3 and ab initio maps as to the qualitative predictions.

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Section: Comparison Ofartemisinin ( I ) (19) (25) (22) (23) and mentioning

confidence: 99%

Computational studies of the structures and properties of potential antimalarial compounds based on the 1,2,4-trioxane ring structure. I. Artemisinin-like molecules

Bérnardinelli

Jefford

Maric

et al. 1994

Int. J. Quantum Chem.

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“…Diesen Erfahrungen entsprechend setzten wir das Dibromocyclopropan 12 in THF in Bei der thermischen Behandlung von 12 erwartet man eine Ringerweiterung des Typs 12 --f 20: Dihalogenocarben-Addukte an Norbornen, Norbornadien und Benzonorbornadien sind namlich thermisch recht labil und gehen (Cyclopropyl-Ally1)-Umlagerungen ein [29]. Es wird angenommen, dass dabei Allyl-Kationen als reaktive Zwischenstufen durchlaufen werden.…”

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Synthese und Pyrolyse einer Triafulven‐Vorstufe

Mühlebach

Neuenschwander

Engel

1993

Helvetica Chimica Acta

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(1 3. IV. 93) Synthesis and Pyrolysis of a Triafulvene PrecursorIn view of retro-Dirk-Alder reactions (RDA reactions), the triafulvene precursor 3 has been prepared in a simple three-step synthesis by dibromocarbene addition at dibenzo-barrelene (11 -+ 12; a%), halogen-Li exchange followed by methylation (12 + 14, 100%) and HBr elimination (14 + 3,62%) (Scheme 3). Reactivity of the so far unknown bridged 1, I-dibromocyclopropane 12 has been explored, including reductions, allylic rearrangements, and 'carbene dimerizations' (Scheme 4 ) . First experiments with respect to the thermal behavior of 3 show that RDA reaction, although occurring in most cases, is not the predominant pathway. When 3 is heated in a sealed tube without solvent, two dimers 26 and 27 are isolated in a total yield of 55% (Scheme 6). On the other hand, gas-phase pyrolysis of 3 at 400' mainly produces rearranged 28 (56%; Scheme 7). It is assumed that bridged trimethylenemethane 29 is an essential intermediate in thermal rearrangements of 3 (Scheme 8).1. Einleitung. -Seit mehr als 20 Jahren wird in verschiedenen Laboratorien versucht, zwei der einfachsten Vertreter der Fulvene und Fulvalene, Triafulven (1) und Calicen (2) zu synthetisieren. Uberraschendenveise blieb Calicen (2) bis heute unbekannt, obwohl es zwei Ringe enthalt, welche sich gegenseitig elektronisch stabilisieren sollten. Andererseits wurden schon recht friih Hinweise darauf erhalten, dass Triafulven als reaktive Zwischenstufe durchlaufen wird [3]. 1981 gelang der erste direkte Nachweis des Grundkor-

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