Publication: Stereocontrolled synthesis of -lactams within [2]rotaxanes: a
showcase of the chemical consequences of the mechanical bonding
Authors
Martinez-Cuezva, Alberto ; Lopez-Leonardo, Carmen ; Bautista, Delia ; Alajarín, Mateo ; Berná Cánovas, José
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Publisher
ACS
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DOI
10.1021/jacs.6b05581
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info:eu-repo/semantics/article
Description
Abstract
The intramolecular cyclization of N-benzyl
fumaramide [2]rotaxanes is described. The mechanical bond of
these substrates activates this transformation to proceed in high
yields and in a regio- and diastereoselective manner giving
interlocked 3,4-disubstituted trans azetidin-2-ones. This activation
effect differs from the common shielding stabilization of threaded
functions through amide-based macrocycles promoting an unusual
and disfavored 4-exo-trig ring closure. Further kinetic and
synthetic studies allowed us to produce an original approach
towards -lactams through a one-pot protocol based on an
intramolecular ring closure followed by a thermally-induced
dethreading step. The advantages for carrying out this cyclization
in the confined space of a benzylic amide macrocycle were
attributed to the anchimeric assistance of the surrounding
macrocycle.
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Citation
J. Am. Chem. Soc. 2016, 138, 28, 8726–8729
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