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For a related process in which the Staudinger reaction has been exploited for the in situ preparation of carbodiimides in the MC sequential synthesis of hydantoins, see:
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For a related process in which the Staudinger reaction has been exploited for the in situ preparation of carbodiimides in the MC sequential synthesis of hydantoins, see:, F. Olimpieri, A. Volonterio, M. Zanda, Synlett 2008, 3016 - 3020.
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78349258123
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note
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With an achiral carbodiimide the reaction is not stereoselective because the stereogenic α-amino acid ester steps in the process once the new stereogenic center is already formed (see the proposed mechanism). However, from the perspective of combinatorial application, the formation of both stereoisomers is not necessarily a drawback. The stereochemistry of the two diastereoisomers was assessed by X-ray diffraction of (S)- 6b (the reported stereochemistry is related to the new stereogenic center formed in the reaction, that is, the stereochemistry of hfVal) and on the basis of their spectroscopic and analytical features. The X-ray structure and relative full details will be published in a full paper.
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-
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41
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78349276882
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note
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[9a]
-
-
-
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42
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0142256048
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The same mechanism has been proposed for a very related reaction, see:, K. Kishikawa, W. Sankhavasi, K. Yoshizaki, S. Kohmoto, M. Yamamoto, K. Yamada, J. Chem. Soc. Perkin Trans. 1 1994, 1205 - 1209.
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Yamada, K.6
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43
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78349249726
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note
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[9b]) and (ii) by treating 9 in acidic media, we observed the formation of hydantoin 14 probably through acid-catalyzed nucleophilic displacement of the alanine moiety by the tert-buyl-NH group.
-
-
-
-
44
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78349231217
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note
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The stereochemistry of the major diastereoisomer was assessed by X-ray diffraction of sugar-peptide conjugate (R)- 13f (see Supporting Information) and on the basis of their spectroscopic and analytical features. Full details will be given in a full paper.
-
-
-
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45
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78349233063
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note
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Also in this case, the diasteroisomeric glycosyl-hydantoin conjugates were recovered as by-products. A detailed study of the synthesis of such compounds will be published in a forthcoming paper.
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