Phosphonates have garnered considerable attention for years owing to both their singular biological properties and their synthetic potential. State‐of‐the‐art methods for the preparation of mixed phosphonates, phosphonamidates, phosphonothioates, and phosphinates rely on harsh and poorly selective reaction conditions. We report herein a mild method for the modular preparation of phosphonylated derivatives, several of which exhibit interesting biological activities, that is based on chemoselective activation with triflic anhydride. This procedure enables flexible and even iterative substitution with a broad range of O, S, N, and C nucleophiles.
A simple and scalable method for stereoselective synthesis of thioethers directly from alcohols using isothiouronium salts is presented. The utility of this thiol-free reaction was exemplified by late-stage modification of complex molecules.
A Brønsted acid-catalyzed selective arene-ynamide cyclization is described. This reaction proceeds via a keteniminium intermediate and enables the preparation of seven-membered ring enamide products. Mechanistic studies uncover an unusual product inhibition behavior.Graphical abstract
Electronic supplementary materialThe online version of this article (10.1007/s00706-018-2320-x) contains supplementary material, which is available to authorized users.
We report the development
of an isothiouronium salt as a reagent
for the operationally simple synthesis of cyanomethyl thioesters with
high functional group tolerance and avoiding the use of thiols. Additionally,
we show that the products can be engaged in amide synthesis in either
a two-step or one-pot fashion.
Phosphonate haben wegen ihrer einzigartigen biologischen Aktivitäten und ihres Synthesepotentials seit Jahren beachtliche Aufmerksamkeit erhalten. Modernste Methoden fürd ie Herstellung von gemischten Phosphonaten, Phosphonamidaten, Phosphonothioaten und Phosphinaten beruhen auf harschen und wenig selektiven Reaktionsbedingungen. Hier wird eine milde Methode zur modularen Herstellung von phosphorylierten Derivaten, viele davon mit interessanten biologischen Aktivitäten, über chemoselektive Aktivierung mittels Trifluormethansulfonsäure-Anhydrid beschrieben. Diese Vorgehensweise ermçglicht eine flexible und sogar iterative Substitution mit einem breiten Spektrum an O-, S-, Nund C-Nukleophilen.
A short approach to chiral diaza-olefines from protected 2,2′-diamino-1,1′-binaphthyl is presented. Cis- and trans-olefines can be selectively obtained by twofold N-allylation followed by RCM or by bridging a 2,2′-diamino-1,1′-binaphthyl precursor with trans-1,4-dibromo-2-butene. Deprotection afforded cis- and trans-dihydro[1,6]diazecines 1 in 58 and 64% overall yield. The reactivity of the but-2-ene-1,4-diyl fragment was investigated yielding corresponding epoxides, diols, and mono- and dibromo products. In several cases rearrangements and participation of the proximate N-Boc group was observed. In no case could allylic substitution be accomplished. From 13 compounds X-ray structure analyses could be obtained.
A method for the Brønsted acid promoted desulfination of aryl sulfoxides is presented. In the presence of a thiol, electron-rich sulfoxides undergo C–S bond cleavage to give the corresponding protodesulfinated arenes and disulfides.
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