Mushroom jack-o’-lantern

Illudins M 112 and S 113 are sesquiterpenes produced by Omphalotus illu-dens, the jack-o -lantern mushroom [149]. These compounds demonstrated in vitro selective toxicity for a wide range of tumor cells compared to normal cells, but poor therapeutic indices were found when tested in vivo [150]. The spiro-cyclopropane and a, -unsaturated ketone moities present in the illudin skeleton constitute a bis-electrophile that is responsible for the DNA damage (vide supra Sect. 2.6) [150,151]. Illudin derivatives with greatly improved therapeutic indices have been prepared first of all dehydroilludin M 114 has shown better... 

Synonym Jack-O-Lantern mushroom [Omphalotus illudens)... 

In another important application of this methodology, ( )-illudin M (79), a toxic sesquiterpene [91,92] isolated from the jack-o -lantern mushroom, has been synthesized [93] by Kinder and co-workers via the spirocyclic carbonyl ylide 48. Rh2 (OAc)4-mediated decomposition of or-diazo ketone 47 in the presence of cyclopentenone 77 afforded the key cycloadduct 78 as a single diastereomer, bearing the complete skeleton of the natural product. Functional group manipulations of the adduct 78 led to a total synthesis of ( )-illudin M (79) (Scheme 23). Padwa and co-workers also executed the syntheses of illudin, ptaquilosin and the closely related isodehydroilludin [78,94] using carbonyl yUdes. This carbonyl ylide cyclization-cycloaddition cascade approach (Scheme 23) has been further extended towards a short synthesis of the acylfulvenes [95], pterosin [79] and pterosin family of sesquiterpenes [96-99]. 

A Reppe type of cocyclotrimerization of the symmetrical diyne 75 with the terminal alkyne 76 was used for synthesis of the isoquinoline natural product illudinine (79), a fungal metabolite from Clitocybe illudens (also known as jack-o-lantern mushroom) (Scheme 7.16) [26]. The Ni(CO)2(PPh3)2 complex (10 mol %) was employed... 

Problem 23.27 Treatment of ethyl acetoacetate with NaOEt (2 equiv) and BrCHgCH2Br forms compound X. This reaction is the first step in the synthesis of illudin-S, an antitumor substance isolated from the jack-o -lantern, a poisonous, saffron-colored mushroom. What is the stmcture of X ... 

The beautiful saffron colored Jack-o -Lantern (CZ/focybe///wr/eos), a poisonous bioluminescent mushroom growing in large clusters during late summer and autumn particularly in the eastern United States, yields an antitumor substance illudin-S shown to possess a unique sesquiterpenoid structure. A total synthesis of Illudin-S has been reported by Matsumoto et al., and involves combination of cyclopropane (A) and cyclopentane (B) moieties of the molecule by Michael addition of a /3-keto sulfoxide, followed by an aldol condensation for completion of the six-membered ring. ... 

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