Selective Photocyclization of Glycine in Dipeptides
β Scribed by Dr. Caroline Wyss; Dipl.-Chem. Rohit Batra; Dr. Christian Lehmann; Dipl.-Chem. Stefan Sauer; Prof. Bernd Giese
- Book ID
- 101557763
- Publisher
- John Wiley and Sons
- Year
- 1996
- Tongue
- English
- Weight
- 346 KB
- Volume
- 35
- Category
- Article
- ISSN
- 0044-8249
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Photocyclizations of dipeptides 5 and 8 occur mainly with retention of configuration at the stereogenic center of alanine. This memory effect of chirality is explained by a hindered rotation in the two intermediate biradicals 9 and 10 that slows down the equilibration of the radicals.
Nickel peroxide selectively cleaves the s-carbon-nitrogen bond of glycine residues in dipeptide derivatives to give the corresponding amides, The glycine selectivity is attributable to preferential complexation of the reactant residue to nickel peroxide and subsequent reaction via a stable o~-centre