Iridomyrmecins

Iridium, dicarbonylcyclopentadienyl-reaction with hexafluorobut-2-yne, 1, 666 Iridomyrmecin crystallography, 3, 624 Iron, bis(borinato)-, 1, 645 Iron, bis(l-methylborinato)-deborination, 1, 645... 

Stereocontrolled syntheses of the natural iridolactone, (-l-)-iridomyrmecine 207 (Eq. 21) and the alkaloid (-)-actinidine 213 (Scheme 24) have been accomplished based on an ISOC reaction as the key step [56,57]. ISOC reaction of 204... 

Antimicrobial, insecticide/insectivorous animals isopr. (iridoid mwioterp.)/ iridomyrmecin r Argentine ant, Irichmyrmex huittilis Mayr., Ins. MI... 

Actinidia arguta (Sieb. et Zucc.) Planch ex Miq. A. chinensis Planch. A. japonica Nakai A. kolomikta (Maxim, ex Rupr.) Maxim. A. polygama (Sieb. et Zucc.) Planch, ex Maxim. Mi Hou Tao (Kiwi) (whole plant) Matatabic acid, iridomyrmecin, actinidine, allomatatabiol, iridomyrmecin, neo-nepetalactone, dihydronepetalactol, matatabiether, isoneomatatabiol, matatabistic acid, neomatabiol, vitamin C, vitamin B.48>50>52 For esophageal and liver cancers, rheumatoid arthritis, arthralgia, urinary stones, fever. 

Iridomyrmecin Actinidia arguta, A. chinensis, A. japonica, A. kolomikta, A. polygama... 

Crystallographic determinations on reduced pyranones include those on iridomyrmecin (171) (64AX472) and the pyran-3-one (172) <82JOC3054>. 

Three other structurally related oxygenated bicyclic molecules are verbenalol (242), iridomyrmecin (247), and forsythide aglycone dimethyl ester (256). All have been synthesized in racemic form. Sakan and Abe s preparative route to 242 is elegantly designed (Scheme 37).301) Readily available ketone 234 was treated in turn... 

The synthesis of iridomyrmecin 247) took advantage of the high transannular reactivity which frequently operates in eight-membered rings (vide supm). To this end, 1,5-dimethyl-1,5-cyclooctadiene 243) was monohydroborated, treated with... 

Lee, E., Yoon, C. H. Stereoseiective Favorskii rearrangement of carvone chiorohydrin expedient synthesis of (+)-dihydronepetaiactone and (+)-iridomyrmecin. J. Chem. See., Chem. Commun. 1994, 479-481. 

Transannulation of the mesylate (33), derived from 4,8-dimethylcycloocta-4-en-l-ol, using sodium carbonate in aqueous dioxane has provided the bicyclo[3.3.0]octanol (34), a central precursor to the monoterpene iridomyrmecin (35 equation 13). In studies of the biomimetic synthesis of the natural tri-quinanes capnellene (37 equation 14) and pentalenene (40 equation IS) Pattenden et al. have shown that both molecules can be produced from appropriate cycloocta-l,S-diene precursors, i.e. (36) and (39) [or indeed their corresponding positional isomers (38) and (41), respectively] by treatment with boron trifluoride. Mehta et al. have described an alternative transannulation approach to the triquinane unit found in pentalenene, i.e. (42) - (43 equation 16), and also to the ring system (44 equation 17) found... 

Eight- to sixteen-step syntheses of isoiridomyrmecin and verbenalol,763 iridomyr-mecin764 allodolicholactone (first synthesis), iridomyrmecin and its iso-epimer785 and sarracenin766 have been reported. 

Snider has shown that thermolysis of 2,6-dimethyl-2,7-octadienal at 350°C yielded three compounds, 365-367, having the iridoid skeleton. The lactone 368 was made by cyclization of the corresponding hydroxy acid ( 8-hydroxy-citronellic acid ), and its tert-butyldimethylsilyl enol ether rearranged in an Ireland-type Claisen rearrangement, yielding the iridoid acid 369 after removal of the silyl group with HF in acetonitrile. The latter was converted (by hydrobora-tion-oxidation) into both isomers of dihydronepetalactone (370) (erroneously considered to be unsynthesized by the authors, who clearly did not read Vol. 4, p. 497). Iridomyrmecin (371) is also accessible from 369 (Scheme 30). 

FIGURE 3 Electron density of iso-iridomyrmecin projected down the 6-axis, (a) Incorrect structure based on low-resolution room temperature data (b) correct structure, based on high-resolution, low-temperature data. From Schoenbom and McConnell.64... 

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