Synthesen in der Isocamphanreihe, 12. Synthese von 8,8‐Dideuteriocamphen

Abstract

Die Synthese von 8,8-Dideuteriocamphen (8) aus Isocamphenilansaure (1) wird beschrieben und die Konstitution von 8 durch spektroskopische Methoden eindeutig festgelegt. Eine friiher postulierte Molekiilumlagerung beim letzten Schritt der Synthese von Camphen (7) wird hierdurch ausgeschlossen, und die Beweisfiihrung fur die konfigurative Zuordnung von (+)-1 zu (-)-7 erscheint damit liickenlos.

Syntheses in the Isocamphane Series XLI [1]. Derivatives of Epoxyisocamphenilanic Acid, Epoxycamphene, and a New Access to 7-syn-Hydroxycamphene

“…We have found a way to transform the carboxyl group at C2 of the bicyclus into the exocyclic double bond of camphene without any arrangement of the sensible monoterpene [17]. On account of the sensitivity of the epoxide function against SOCl 2 , the conventional way to prepare an acid amide was not possible.…”

Syntheses in the Isocamphane Series XLII [1]. Synthesis and Odour of 5-exo-Hydroxycamphene (Isonojigiku Alcohol)

“…[14]) prompted us to use 7 in the synthesis of the target compound 6 as well. However, several attempts to prepare 5-hydroxycamphene (6) via hydroxylation of the endocyclic double bond of 7 followed by the already established reaction sequence to transform the side chain of 7 into the exocyclic double bond [1,15] failed. An unseparable 1:2 mixture of the corresponding 5-hydroxy-and 6-hydroxydimethylnorbornane compounds was obtained using different hydroxyl protecting groups (e.g.…”

Palladium catalyzed transformations of monoterpenes: stereoselective deuteriation and oxidative dimerization of camphene

“…c Deuteriated exclusively at position 8a. d Deuteriated at positions 8a and 8b (described previously in[27]). e Camphene-d 1 deuteriated at position 8b (2% of reacted camphene, signal from H-8a at 4.69 ppm) and diene 2 (10% of reacted camphene) are detected.…”