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involvement of (R)-NPP in the BbS-catalysed reaction, where-
as diphosphate was selectively eliminated from (S)-NPP by BbS
to yield 1. The selectivity is understandable by the fixed, chiral
active site architecture of BbS promoting ring closure only for
(R)-NPP. In future studies, this experimental approach will not
only provide insights into the stereochemical identity of inter-
mediates in cases of achiral terpenes inhibiting any conclusion
from the product structure as shown here, but will also deepen
our knowledge of general NPP utilisation by sesquiterpene
synthases. The chirality of this tertiary diphosphate is currently
largely underinvestigated in the characterisation of TSs, even
for cascades requiring its involvement.
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Supporting Information
Experimental details of culture conditions, gene cloning,
protein purification, incubation experiments, isolation of 5
and HPLC purifications, the amino acid sequence of BbS, a
phylogenetic tree with the location of BbS, SDS-PAGE
analysis, listed NMR data of 5, labelling experiments for
NMR assignment, synthetic procedures for the NPPs,
Mosher ester analysis of epoxides, and chiral GC analysis
of nerolidols.
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Klapschinski, T. A.; Janusko, A.; Dickschat, J. S.
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Acknowledgements
This work was funded by the Deutsche Forschungsgemein-
schaft (DI1536/7-1). We thank Andreas J. Schneider for HPLC
purifications.
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