萜类：规则的异戊二烯－有机化学课件.ppt

26.7Terpenes: The Isoprene Rule Terpenes Terpenes are natural products that are structurally related to isoprene. Terpenes Myrcene (isolated from oil of bayberry) is a typical terpene. The Isoprene Unit An isoprene unit is the carbon skeleton of isoprene (ignoring the double bonds) The Isoprene Unit The isoprene units of myrcene are joined head-to-tail. Table 26.2 Class Number of carbon atoms Monoterpene 10 Sesquiterpene 15 Diterpene 20 Sesterpene 25 Triterpene 30 Tetraterpene 40 Figure 26.6 Figure 26.6 Figure 26.6 Figure 26.6 Figure 26.6 Figure 26.6 Figure 26.6 Figure 26.6 Figure 26.6 Figure 26.6 26.8Isopentenyl Pyrophosphate:The Biological Isoprene Unit The Biological Isoprene Unit The isoprene units in terpenes do not come from isoprene. They come from isopentenyl pyrophosphate. Isopentenyl pyrophosphate (5 carbons) comes from acetate (2 carbons) via mevalonate (6 carbons). The Biological Isoprene Unit Isopentenyl Pyrophosphate Isopentenyl and Dimethylallyl Pyrophosphate Dimethylallyl pyrophosphate has a leaving group (pyrophosphate) at an allylic carbon; it is reactive toward nucleophilic substitution at this position. 26.9Carbon-Carbon Bond Formation in Terpene Biosynthesis Carbon-Carbon Bond Formation The key process involves the double bond of isopentenyl pyrophosphate acting as a nucleophile toward the allylic carbon of dimethylallyl pyrophosphate. Carbon-Carbon Bond Formation After C—C Bond Formation... The carbocation can lose a proton to give a double bond. After C—C Bond Formation... The carbocation can lose a proton to give a double bond. After C—C Bond Formation... This compound is called geranyl pyrophosphate. It can undergo hydrolysis of its pyrophosphate to give geraniol (rose oil). After C—C Bond Formation... From 10 Carbons to 15 From 10 Carbons to 15 From 10 Carbons to 15 This compound is called farnesyl pyrophosphate. Hydrolysis of the pyrophosphate ester gives the alcohol farnesol (Figure 26.6). From 15 Carbons to 20 Farnesyl pyrophosphat