Jack O Lantern

P. olearius ( Jack O Lantern several synonyms, including Clitocybe illudens and Ompbalotus olearius), P. japonicus (syn. Lampteromyces japonicus), P. noctilucens... 

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... 

Occurrence.—The pale glow which hovers over marshes, and which, under the name of will o the wisps, Jack o lanterns, etc., has been the subject of many legends, has been attributed to traces of phosphine with other gases produced by the decomposition of organic matter. This is rendered probable by the observation that phosphine is produced by the putrefaction of proteins.1... 

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 jack-o -lantern, source of the antitumor agent illudin-S... 

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

The word jack-o -lantern may have come from the legend of Irish Jack, a mean old man in life, he was condemned after death to wander the earth carrying a hollow turnip with a lump of burning coal inside. 

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]. 

Wagner BD, Fitzpatrick SJ, Gill MA, MacRae AI, Stojanovic N. A fluorescent host-guest complex of cucurbituril in solution a molecular jack o lantern. Can J Chem 2001 79 1101-4. 

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... 

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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