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Issue 47, 2018
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Chiral [16]-ane P4N2 macrocycles: stereoselective synthesis and unexpected intermolecular exchange of endocyclic fragments

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Abstract

Chiral 1,9-diaza-3,7,11,15-tetraphosphacyclohexadecanes were stereoselectively synthesized as pure RPSPSPRP isomers via a one-pot Mannich-type condensation reaction of 1,3-bis(arylphosphino)propane, formaldehyde and optically active, as well as racemic, primary amines. An unprecedented intermolecular exchange of endocyclic amino fragments of 1,9-diaza-3,7,11,15-tetraphosphacyclohexadecanes was observed. The lability of the P–CH2–N fragment in macrocyclic aminomethylphosphines is the reason of the stereoisomerization, formation of products with medium-sized cycles as well as the exchange of endocyclic amino fragments. The mechanism of these transformations involving the formation of a methylenephosphonium intermediate and further intra- and intermolecular nucleophilic substitution is discussed.

Graphical abstract: Chiral [16]-ane P4N2 macrocycles: stereoselective synthesis and unexpected intermolecular exchange of endocyclic fragments

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Publication details

The article was received on 06 Aug 2018, accepted on 14 Nov 2018 and first published on 19 Nov 2018


Article type: Paper
DOI: 10.1039/C8DT03214A
Citation: Dalton Trans., 2018,47, 16977-16984
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    Chiral [16]-ane P4N2 macrocycles: stereoselective synthesis and unexpected intermolecular exchange of endocyclic fragments

    E. I. Musina, R. N. Naumov, K. B. Kanunnikov, A. B. Dobrynin, S. Gómez-Ruiz, P. Lönnecke, E. Hey-Hawkins, A. A. Karasik and O. G. Sinyashin, Dalton Trans., 2018, 47, 16977
    DOI: 10.1039/C8DT03214A

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