Ireland-Claisen Rearrangement of 6-Methylene-1,4-oxazepan-2-ones

European Journal of Organic Chemistry 2015
Gints Šmits, Artis Kinēns, Rolands Zemribo

The Ireland-Claisen rearrangement of 6-methylene-1,4-oxazepan-2-one-derived boron enolates leads to stereochemically defined, synthetically useful 4-(E)-ethylidene prolines. Detailed computational and experimental studies explain the stereochemical outcome of this transformation and suggest an unusual double-chelated transition state that involves two boron atoms. The scope of the method is also explored.

Keywords
Amino acids | Boron | Density functional calculations | Natural products | Sigmatropic rearrangement | Transition states
DOI
10.1002/ejoc.201500918

Šmits, G., Kinēns, A., Zemribo, R. Ireland-Claisen Rearrangement of 6-Methylene-1,4-oxazepan-2-ones. European Journal of Organic Chemistry, 2015, Vol.2015, Iss.30, pp.6701-6709. ISSN 1434-193X. e-ISSN 1099-0690. Available from: doi:10.1002/ejoc.201500918

Publication language
English (en)