Reaction: littorine + [reduced NADPH—hemoprotein reductase] + O2 = hyoscyamine aldehyde + [oxidized NADPH—hemoprotein reductase] + 2 H2O (overall reaction)
(1a) littorine + [reduced NADPH—hemoprotein reductase] + O2 = 3-hydroxylittorine + [oxidized NADPH—hemoprotein reductase] + H2O
(1b) 3-hydroxylittorine = hyoscamine aldehyde + H2O (spontaneous)
For diagram of reaction click here and mechanism click here.
Other name(s): CYP80F1
Systematic name: littorine,[reduced NADPH—hemoprotein reductase]:oxygen oxidoreductase (hyoscyamine aldehyde forming)
Comments: Isolated from the plants Hyoscyamus niger (black henbane) and Anisodus acutangulus. Involved in the biosynthesis of the alkaloids hyoscyamine (atropine) and scopalamine. The reaction involves hydroxylation of littorine, giving a 1,2-diol that undergoes a spontaneous dehydration accompanied by pinacol rearrangement.
Links to other databases: BRENDA, EXPASY, KEGG, MetaCyc, CAS registry number:
References:
1. Li, R., Reed, D.W., Liu, E., Nowak, J., Pelcher, L.E., Page, J.E. and Covello, P.S. Functional genomic analysis of alkaloid biosynthesis in Hyoscyamus niger reveals a cytochrome P450 involved in littorine rearrangement. Chem. Biol. 13 (2006) 513-520. [PMID: 16720272]
2. Sandala, G.M., Smith, D.M. and Radom, L. The carbon-skeleton rearrangement in tropane alkaloid biosynthesis. J. Am. Chem. Soc. 130 (2008) 10684-10690. [PMID: 18627156]
3. Nasomjai, P., Reed, D.W., Tozer, D.J., Peach, M.J., Slawin, A.M., Covello, P.S. and O'Hagan, D. Mechanistic insights into the cytochrome P450-mediated oxidation and rearrangement of littorine in tropane alkaloid biosynthesis. Chembiochem 10 (2009) 2382-2393. [PMID: 19693762]
4. Cui, L., Huang, F., Zhang, D., Lin, Y., Liao, P., Zong, J. and Kai, G. Transcriptome exploration for further understanding of the tropane alkaloids biosynthesis in Anisodus acutangulus. Mol. Genet. Genomics 290 (2015) 1367-1377. [PMID: 25876163]