ChemComm
Communication
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Scheme 1 Plausible mechanism for the synthesis of g-lactams 3.
Corey–Chaykovsky reaction10 was established based on the
stoichiometric sulfur ylide-mediated epoxidation reported in 1958
by Johnson and LaCount.24 Since then, many improvements have
been made to this reaction. It is widely known that such reaction
involves the attack of an ylide on a carbonyl group, which yields a
betaine intermediate that collapses to give an epoxide and a
sulfide.25 In contrast to these reports, Kumar and co-workers
recently investigated Corey–Chaykovsky reaction of aldehydes and
revealed that no epoxide intermediate was formed during the
reaction process.26 Actually, such an epoxide intermediate was not
detectable within our reaction system.
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On the basis of the reported literature and our obtained results, a
mechanism was proposed for the synthesis of g-lactams 3 as
depicted in Scheme 1. In the presence of sodium hydride, trimethyl-
sulfoxonium iodide 2 is converted into sulfur ylide, i.e. Corey–
Chaykovsky reagent.25c The attack of the in situ generated sulfur
ylide on the carbonyl group of 1 gives rise to a betaine intermediate
A, which is in turn followed by facile proton exchange from the
carbamate nitrogen to the basic oxide ion to afford the stable species
B.26,27 The final product, g-lactams 3, is formed after the intra-
molecular lactamization of B with the elimination of DMSO.26,28
In summary, a facile and efficient synthesis of b-hydroxy-
g-lactams 3 from readily available a,a-dialkyl b-oxo amides 1 and
trimethylsulfoxonium iodide 2 via a tandem Corey–Chaykovsky
reaction and an intramolecular lactamization process has been
developed. The ready availability of substrates, mild reaction condi-
tions, simplicity of execution, high yields and synthetic potential of
the products make this protocol much attractive. Further work on
the utilization and extension of the scope of the protocol is currently
underway in our laboratory.
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22 For the X-ray diffraction analysis of 3p and 3u, see ESI†.
23 The relative stereochemistry of the major diastereoisomer of 3w was
confirmed by NOESY NMR studies. A significant NOESY correlation
was observed between HC and HC , and the correlation between HC
1
1
and HC was not detected, both2 suggesting the syn relationship
3
between C1 and C2 (see below).
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Financial support of this research by the National Natural
Science Foundation of China (20872136 and 51073150) is
greatly acknowledged.
Notes and references
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c
7360 Chem. Commun., 2013, 49, 7358--7360
This journal is The Royal Society of Chemistry 2013