Characterization and Engineering of a Bisabolene Synthase Reveal an Unusual Hydride Shift and Key Residues Critical for Mono-, Bi-, and Tricyclic Sesquiterpenes Formation.

Sesquiterpene synthases (STSs) catalyze carbocation cascade reactions with various hydrogen shifts and cyclization patterns that generate structurally diverse sesquiterpene skeletons. However, the molecular basis for hydrogen shifts and cyclizations, which determine STS product distributions, remains enigmatic. In this study, an elusive STS SydA was identified in the biosynthesis of sydonol, which synthesized a new bisabolene-type sesquiterpene with a unique saturated terminal pendant isopentane.

Cytotoxic Stilbenoids, Hetero- and Homodimers of Homoisoflavonoids from .

An activity-guided isolation study on the EtOH extract prepared from the bulbs of yielded four new phenolic compounds, including a new stilbenoid (), a new homoisoflavonoid derivative (), a new homoisoflavonoid dimer (), and an unprecedented homoisoflavone-stilbene heterodimer (), together with six known (-) analogs. Their chemical structures were elucidated by spectroscopic analysis and theoretical NMR and ECD calculations. Compounds and are unique in their scaffolds.

Docking carbocations into terpene synthase active sites using chemically meaningful constraints-The TerDockin approach.

Terpenes are a diverse class of natural products which have long been sought after for their chemical properties as medicine, perfumes, and for food flavoring. Computational docking studies of terpene mechanisms have been a challenge due to the lack of strong directing groups which many docking programs rely on. In this chapter, we dive into our computational method Terdockin (Terpene-Docking) as a successful methodology in modeling terpene synthase mechanisms.