Caryophyllanes

Approximately 30 naturally abundant caryophyllanes are derived from humulanes in which C-2 and C-10 close a cyclobutane ring. 

Other representatives include (-)-6,7-epoxy-3(15)-caryophyllene from the leaves, flowers and stems of cloves, (+)-6-caryophyllen-15-al from the oil of sage (Salvia sclarea, Labiatae), and (-)-3(15),7-caryophylladien-6-ol from Indian hemp Cannabis saliva var. indica (Cannabaceae). 

The absolute configuration of caryophyllene (255) found in Scapania undulata was the same as that isolated from tracheophytes (2). Andersen and coworkers (2) suggested that (255) might be arised from trans-trans-farnesyl pyrophosphate in S. undulata. Caryophyllene is one of the common sesquiterpene hydrocarbons in the Hepaticae, particularly in the Frullaniaceae (27). 

Chart 10. Curcumenes, calacorenes, caryophyllenes, and cedrenes found in he Hepaticae References, pp. 269—285 

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As indicated in Figure 3, the cadlnanes (170 - 187) are formed from the humulane (205) system, which also is the progenitor of the caryophyllanes (206 - 208). Of these last three compounds, caryophyllene (206) itself is of particular Importance, since it can account for 20 - 25% of the essential oil of some samples (lA). Other major constituents in the same sample were copaene (173, another cadinane) and a-humulene (205), each near 15%. It is therefore apparent that the pathway involving initial conversion of Z,E-farnesyl pyrophosphate to the humulane system is dominant in Gossypiwn terpenoid biogenesis. 

Several sesquiterpene skeletons include cyclobutane rings [78]. Some representative examples are summarized in Sch. 20. As can be easily seen, syntheses of caryophyllanes 78 and panasinsanes 79 are based on photocycloadditions to 2-methylpropene, those of tritomaranes (kelsoanes) 80, protoilludanes 81, and sterpuranes 82 are based on photocycloadditions to ethylene, while the bourbonane skeleton 83 is accessible via... 

Fattorusso, C. Stendardo, E. Appendino, G. Fattorusso, E. Luciano, P. Romano, A. Taglialatela-Scafati, O. Artarborol, a nor-caryophyllane sesquiterpene alcohol from artemisia arborescens. Stereostructure assignment through concurrence of NMR data and computational analysis, Org. Lett. 2007, 9, 2377-2380. 

Caryophyllane, Humulane, Africane, Illudalane, Protoilludane, Hirsutane, Vellerane, Pentalane, Senoxydane... 

Humulane, Caryophyllane, Protoilludane, Illudane, Marasmane, Hirsutane... 

The proposed intermediacy of humulene (218) in the biosynthesis of sesquiterpenoids belonging to various structural groups (caryophyllane, protoilludane, etc.)... 

This unusual monosaccharide is the repeating unit of the O-chain of the main LPS of B. caryophylli, called caryophyllan [Fig. (5)]. It proved to be a linear homopolysaccharide built up of (l->7) a-caryophyllose, as deduced from GC-MS analysis of the products of hydrolysis, reduction and acetylation of the methylated LPS. 

When the H and 13C NMR spectra of the hydrolysed LPS fraction were recorded, the presence of a further anomeric signal, not attributable to the completely hydrolysed caryophyllan, was observed. The O-chain structure of the new LPS, called caryan, was determined by applying the... 

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