Synthesis of ferrocenyl conjugates of thio analogs of hydroxyl-containing biomolecules via the Mitsunobu reaction with N-(ethoxycarbonyl)ferrocenecarbothioamide as the pronucleophile

Mitsunobu and Related Reactions: Advances and Applications

“…Reaction of N -(2-hydroxyethyl)- N ′-phenylthioureas under Mitsunobu conditions gave both N - and S -cyclized products . Selective sulfur alkylations leading to cyclic thioethers 461 and tricyclic pyrrolo[2,3- d ]pyrimidine 462 have also been reported (Scheme b and c). , A similar S -alkylation has been utilized by Wrona and Zakrzewski for the synthesis of ferocenyl conjugates of cholesterol and stigmasterol . Other applications involving thioether formation involve the synthesis of (i) phosphonylated thiazolines, (ii) thioalkylated pyrimidine nucleosides, (iii) methyl 5′-thio-α-isomaltoside, (iv) curacin A, and (v) 8,2′- S -cyclopurinenucleoside …”

N-(ethoxycarbonyl)ferrocenecarboxamide: Synthesis and use as the pronucleophile in the Mitsunobu reaction

“…It found a number of applications in the ferrocene chemistry for transformation of ferrocenyl alcohols into other derivatives [5e10]. In contrast, to our knowledge there is only one report on the Mitsunobu reaction with a ferrocenyl pronucleophile [11]. We found that N-(ethoxycarbonyl)ferrocenecarbothioamide 1 is sufficiently acidic to form under the Mitsunobu conditions the conjugated anion, which undergoes S-alkylation with alcohols (Scheme 1).…”

Phosphines and related C–P bonded compounds

“…289 A review has appeared of the use of the triphenylphosphine-DEAD reagent for the synthesis of carbon-nitrogen bonds through a variety of reactions that extend its role beyond the familiar Mitsunobu reaction. 290 New applications of Mitsunobu procedures include an efficient, one-pot route to trithiocarbonates from thiols, 291 a new route for the attachment of a ferrocenyl moiety to hydroxy-functionalised biomolecules, 292…”