Coriolus consors

In 1976, Nozoe, et al. isolated and identified hirsutene (651) from an extract of the mycelium of Coriolus consors. Matsumoto has described the transformation of the protoilludene 652 and humulene (653) into 651 and other compounds... 

Coriolin (689), a metabolite of the Basidiomycete Coriolus consors, has attracted widespread interest because of its unusual anti-tumor activity and highly functionalized triquinane structure. Accordingly, a number of syntheses of689 have appeared on the scene. One of the earliest, due to Tatsuta, et al., begins with epoxide 690, whose preparation had been earlier realized in connection with their work on hirsutine (see Scheme LXIII). Deoxygenation of 690, hydrolysis, and cis-hydroxy-lation provided keto triol 691 (Scheme LXXII) The derived acetonide was transformed via 692 into tetraol 693 which could be selectively acetylated and dehydrated on both flanks of the carbonyl group. Deacetylation of 694 followed by epoxidation completed the synthesis. 

The suggested intermediacy of hirsutene (239) in the biosynthesis of the hirsutane sesquiterpenoids has been supported by its recent isolation from Coriolus consors. In addition an alternative synthesis of this compound has been accomplished by the route outlined in Scheme 26. 

Previously identified and new sesquiterpenoids were isolated from an unidentified fungus obtained from an Indo-Pacific sponge Jaspis aff. Johnstoni [103,104]. The mycelium gave coriolin B (76 extraction yield 3.8 mg/1) and dihydrocoriolin C (77 extraction yield 3.7 mg/1), which were previously reported from the terrestrial basidiomycete Coriolus consors. The broth gave chloriolin A (78 a white crystal extraction yield 4 mg/1), chloriolin B (79 a white solid extraction yield 3.5 mg/ml) and chloriolin C (80 a white solid extraction yield 0.6 mg/ml). The structure of these three new chlorinated compounds was determined by NMR experiments, synthetic transformations and X-ray crystallography. 

Another member of the hirsutane family of sesquiterpenes, coriolin (65), which is a metabolite of Coriolus consor, has yielded to total synthesis. Key steps in the approach to coriolin by Danishefsky et al. include the conversion of (61) into (63) via the Diels-Alder adduct (62), and introduction of the hydroxyl group into ring B by deconjugation of the enone (64) followed by epoxidation of the isolated double bond (Scheme 10). 

The tricyclic hydrocarbon hirsutene (94), isolated recently from Coriolus consors, is a probable precursor for coriolin (95), found in C. consors, and also for hirsutic acid (96), isolated from Stereum hirsutum. In a biogenetically patterned synthesis of hirsutene, Ohfume et al. have shown that treatment of the tricyclic hydrocarbon (92) with a catalytic amount of toluene-p-sulphonic acid leads to the endo-isomer (93), in 95% yield, which by manipulation of the double bond can be... 

Corey-Chaykovsky reaction 318 Coriolus consors 800 counteranions 437... 

Wang, G.-Y-S., Abrell, L.M., Avelar, A., Borgeson, B.M., and Crews, P. (1998) New hirsutane based sesquiterpenes from salt water cultures of a marine sponge-derived fimgus and the terrestrial fungus Coriolus consors. Tetrahedron, 54, 7335-7342. 

Since intramolecular transannular aldol reactions create two new rings and at least two new stereogenic centers in a single process, the corresponding cyclic p-hydroxy ketones are useful for the synthesis of polycyclic natural products. The trons-4-fluoro proline 48 is superior to (S)-proline in catalysis of this type of reaction, affording excellent diastereoselectivity and enantioselectivity (Scheme 28.4). The utility of this reaction has been demonstrated in a total synthesis of (-l-)-hirustene (50), is a fungal metabolite first isolated from the basidiomycete Coriolus consors [27]. 

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