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tion between two intramolecular ylide-forming pathways,
namely the formation of cyclic sulfonium and carbonyl ylides.
To this end, 2-diazo-3-oxo-4-phthalimidocarboxylic esters 8a–c
were prepared from the mercapto-functionalised aminoacids
methionine, S-benzylcysteine, and S-allylcysteine. Rhodium(II)-
catalysed decomposition of the diazoesters was found to
produce both six- or five-membered cyclic sulfonium ylides and
six-membered carbonyl ylides. In a qualitative manner, it can be
stated that in the case of 8a formation of the six-membered
cyclic carbonyl ylide 14a clearly supersedes the formation of
the six-membered sulfonium ylide 12a, although the struc-
turally analogous cyclic sulfonium ylide 20 is formed quantita-
tively from diazoester 11a, which bears no phthalimido group.
This result is confirmed by the absence of 12a from the reac-
tions in which the carbonyl ylide was intercepted by intermolec-
ular [3 + 2] cycloaddition with the dipolarophiles NPI and
DMAD (notice that carbonyl ylide dimer 13a also results from
an intermolecular cycloaddition reaction). With the cysteine-
derived diazoesters 8b and c, on the other hand, it appears that
the formation of the five-membered cyclic sulfonium ylides 12b
and c and of the six-membered cyclic carbonyl ylides 14b and c
is about equally efficient. Interestingly, the S-allyl group
spontaneously transforms both types of ylides into non-ylidic
products, namely by [2,3]-sigmatropic rearrangement for the
S-ylide and intramolecular [3 + 2]-cycloaddition for the carbon-
yl ylide.
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Supporting Information
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The supporting information contains experimental
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Acknowledgements
We thank Dr. Ulrich Jäger and Professor Willi Kantlehner
(Hochschule Aalen) for the high-resolution ESI mass spectra.
27.Weingarten, M. D.; Prein, M.; Price, A. T.; Snyder, J. P.; Padwa, A.
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