Solid-Supported Heterocumulenes:  Preparation and Crystal Structure of Azaaplysinopsins

Abstract

Annulation of carbodiimides 6a,b, on alumina solid support, selectively gives (Z)-hydantoins 8a,b determined on the basis of X-ray analysis while thermal cyclization affords, after purification, 8a,b with imidazolones 10a,b. In the imidazopyrimidine series, thermal reaction of heterocumulenes 6d yields, via a Dimroth rearrangement, the dipyridoimidazolic compound 11. In all cases, mechanisms for the observed cyclizations have been proposed.

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“…calc. for C 15 4'-Allyl-3'-deimino-2',4'-bis(demethyl)-2-methyl-3'-thioxoaplysinopsin ( 3-Allyl-5-[(2-methyl-1H-indol-3yl)methylidene]-2-thioxoimidazolidin-4-one; 18h). Prepared from allyl isothiocyanate and 14b; 4 h; 40% (100% (Z)).…”

“…This has been cyclized by treatment with nitrogen nucleophiles, such as ammonia, aliphatic amines, and hydrazines to give aplysinopsin derivatives [13]. In this context, a highly effective method for the synthesis of aza-carboline and aza-aplysinopsin mimic structures from heterocumulenes [14] and from alumina-supported heterocumulenes [15] have also been reported.…”

Group 2 Catalysis for the Atom‐Efficient Synthesis of Imidazolidine and Thiazolidine Derivatives

“…The imidazolidine‐2,4‐dione (hydantoin) moiety is a particularly notable constituent of many biologically active compounds and numerous hydantoin derivatives have been identified as anticonvulsant, antiulcer, antiarrhythmic, antimuscarinic, antiviral and antidiabetic agents 2. For example, phenytoin is commonly used in the treatment of epilepsy3 and aplysinopsin, isolated from the sponge Aplysinopsis reticulate , has been shown to exhibit cytotoxicity against cancer cells 4. The agonist of the human‐androgen receptor, GLPG04924,5 and the hydantoin muscle relaxant, dantrolene,6 have been widely employed in a medical context.…”

One‐pot synthesis of new hydantoin (thiohydantoin) derivatives and evaluation of their antibacterial and antioxidant activities

“…It is found in the skeleton of many natural compounds extracted from sponges, corals, and marine organisms. [1][2][3][4][5][6] Various biological and pharmacological activities have been reported for hydantoin derivatives, such as antibacterial, [7] antiviral, [8] anticonvulsant, [9,10] antiarrhythmic, [11] antiandrogen, [12] platelet aggregation inhibitory, [13,14] and antidiabetic [15] activities. Also, thiohydantoin derivatives have been found in hypolipidemics, [16] anticarcinogenics, [17] antimutagenics, [18] antithyroidals, [19] antivirals, [20,21] antimicrobials, [22,23] anti-ulcer and anti-inflammatories, [24] as well as herbicides.…”