- Biocatalytic One-Carbon Ring Expansion of Aziridines to Azetidines via a Highly Enantioselective [1,2]-Stevens Rearrangement
-
We report enantioselective one-carbon ring expansion of aziridines to make azetidines as a new-to-nature activity of engineered "carbene transferase" enzymes. A laboratory-evolved variant of cytochrome P450BM3, P411-AzetS, not only exerts unparalleled stereocontrol (99:1 er) over a [1,2]-Stevens rearrangement but also overrides the inherent reactivity of aziridinium ylides, cheletropic extrusion of olefins, to perform a [1,2]-Stevens rearrangement. By controlling the fate of the highly reactive aziridinium ylide intermediates, these evolvable biocatalysts promote a transformation which cannot currently be performed using other catalyst classes.
- Miller, David C.,Lal, Ravi G.,Marchetti, Luca A.,Arnold, Frances H.
-
supporting information
p. 4739 - 4745
(2022/03/27)
-
- On the "Normalizing Factor" for the Tomato Mutant chloronerva, XX - Homologues of Nicotianamine
-
The syntheses of the nicotianamine homologues (2S,αS)-α-amino>-2-carboxy-1-azetidinepentanoic acid (8) and the corresponding proline compound 11 were achieved by stepwise combination of the ethyl esters of (S)-2-azetidinecarboxylic acid or (S)-proline with ethyl (S)-5-oxo-2-(trifluoroacetylamino)pentanoate (4) via reductive coupling.The amino acids 8 and 11 exhibit no biological effect on the phenotypical normalization of the tomato mutant chloronerva.
- Ripperger, Helmut,Schreiber, Klaus,Faust, Juergen
-
p. 301 - 306
(2007/10/02)
-