Contribution A L'étude des Composés Sesquiuterpéniques. V. — Structure du Bicyclovétivénol et du Véticadinol, Alcools Tertiaires de L'Huile de Vétiver du Congo

Chiurdoglu, Grégoire; Delsemme, Antoine

doi:10.1002/bscb.19610700102

Cited by 8 publications

References 11 publications

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Stereoselektiver Aufbau von trans‐Decalinen über intramolekulare En‐Reaktionen; Synthese des enantiomerenreinen Cadinan‐Sesquiterpens Veticadinol

et al. 1988

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nen nahezu idealen Khombus (Winkelsumme des Vierringes = 359.4'). Das RhZ-Atom ist um 55.7" aus der Ebene eines planaren Funfringes abgeknickt. In bezug auf Formalladungen w2re anstelle von P : " und d8,d6-Rh auch die Alternative P: " und d6,d"-Rh diskutierbar. 4 konnte sich auch aus [($-P,,)RhCp*], einem Sandwichkomplex rnit dem Phosphor-Analogon des Cyclobutadiens als Ligand, durch oxidative Addition (Offnung einer P-P-Kante) gebildet haben. At b. I. Struktur von 4 i m Kristall. Ausgewrihlte Bindungslangen [A\ und -wnkel ["I. R h l -P I 2.381(2), Rhl-P2 2.392(2). Rhl-P3 2.387(2), Rhl-P4 Q VCH ~etIuysyesell.~chuf~ mhH. 0-6940 Weinheirn. 1986 0044-8249/88/0505-0740 S 02.SON Anyew. 5: Veticadinol 2, dessen Slruktur bisher nicht 2.weifelsfrei hewiesen ist, wurde von Chiurdoglu und Delsemme aus kongolesischem Vetiverol isoliert. Der Versuch, 2 in VetiverBl ,,Bourbon", das uns zur Verfiigung geslellt worden war, durch GC-MS-Analyse nach siulenchromatographischer Vorreinigung nachzuweisen, verlief negativ.

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Stereoselektiver Aufbau von trans‐Decalinen über intramolekulare En‐Reaktionen; Synthese des enantiomerenreinen Cadinan‐Sesquiterpens Veticadinol

et al. 1988

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Stereoselective Synthesis of trans‐Decalins via Intramolecular Ene Reactions; Synthesis of the Enantiomerically Pure Cadinane‐Sesquiterpene Veticadinol

Tietze

Beifuß

Antel

et al. 1988

Angew. Chem. Int. Ed. Engl.

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Quantum chemical ab-initio calculations (SCF, 3-21Gbasis set. experimental geometry), were carried out for 3 and the monoanion 3a, as well as for 1 and its monoanion la, in order to ascertain the reason for the markedly different acidities of the compounds 1 and 3. The deprotonation energy of 1 was calculated to be 1573 kJ mol-', and that of 3 to be only 1452 kJ mol-'. This result is understandable on the basis of population analyses according to Mulliken, which show a stronger delocalization of the additional electron in the bicyclic 3a than in l a .The question whether measured structural data (aplanarity of the bicyclic compound) are to be interpreted as molecular properties or must be attributed to packing effects in the crystal, could also be settled by quantum chemical calculations for 3, the dianion 3b,["] and 8. Comparison of a pyramidal and a planar environment for the nitrogen atom shows that planarity of the central R2N-NR2 fragment is more favorable for the molecules 3, 3b, and 8 : the relative stabilities for a planar R2N-NR2 fragment are + 25.3 for 8 (folding angle as in 3), + 15.5 for 3, and + 5.9 kJ mol-.' for 3b. Therefore the folding angles observed in 3 and 3b in the crystalline state can be attributed to intermolecular interactions and to neighboring cations, respectively.Experimental 6 : A solution of 4 (30 g, 94.4 mmol) in CHIC12 (50 mL) was cooled to -60°C in the absence of moisture in a three-necked flask fitted with a cooled dropping funnel. I 1 g (155.1 mmol) of chlorine (ca. 7 mL at -60°C) were condensed into the dropping funnel and added dropwise within I h to the solution of 4, which turned deep red in color. All volatile components were then removed under vacuum and the temperature slowly raised to 0°C (great care must be taken here: vigorous evolution of CI2 takes place spontaneously at ca. -40°C); 6 separated out thereby in the form of red crystals.

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Chemical constituents of the essential oil of the hornwort Anthoceros caucasicus

Sonwa

König

2003

Flavour & Fragrance J

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Contribution A L'étude des Composés Sesquiuterpéniques. V. — Structure du Bicyclovétivénol et du Véticadinol, Alcools Tertiaires de L'Huile de Vétiver du Congo

Cited by 8 publications

References 11 publications

Stereoselektiver Aufbau von trans‐Decalinen über intramolekulare En‐Reaktionen; Synthese des enantiomerenreinen Cadinan‐Sesquiterpens Veticadinol

Stereoselektiver Aufbau von trans‐Decalinen über intramolekulare En‐Reaktionen; Synthese des enantiomerenreinen Cadinan‐Sesquiterpens Veticadinol

Stereoselective Synthesis of trans‐Decalins via Intramolecular Ene Reactions; Synthesis of the Enantiomerically Pure Cadinane‐Sesquiterpene Veticadinol

Chemical constituents of the essential oil of the hornwort Anthoceros caucasicus

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