Biosynthesis and Conformational Properties of the Irregular Sesquiterpenoids Isothapsadiene and β‑Isothapsenol

A carbocation cyclization/rearrangement mechanism for the biosynthesis of isothapsadiene and β-isothapsenol is shown to be energetically viable on the basis of density functional theory (DFT) calculations. In addition, for both isothapsadiene and β-isothapsenol, variable-temperature NMR experiments reveal two equilibrium conformers that undergo hindered exchange. The identities of these conformers, which are related by a chair-flip, are confirmed by DFT calculations on their structures, energies, ¹H and ¹³C chemical shifts, and interconversion pathways

Biosynthesis and Conformational Properties of the Irregular Sesquiterpenoids Isothapsadiene and β‑Isothapsenol

A carbocation cyclization/rearrangement mechanism for the biosynthesis of isothapsadiene and β-isothapsenol is shown to be energetically viable on the basis of density functional theory (DFT) calculations. In addition, for both isothapsadiene and β-isothapsenol, variable-temperature NMR experiments reveal two equilibrium conformers that undergo hindered exchange. The identities of these conformers, which are related by a chair-flip, are confirmed by DFT calculations on their structures, energies, ¹H and ¹³C chemical shifts, and interconversion pathways

Biosynthesis and Conformational Properties of the Irregular Sesquiterpenoids Isothapsadiene and β‑Isothapsenol

A carbocation cyclization/rearrangement mechanism for the biosynthesis of isothapsadiene and β-isothapsenol is shown to be energetically viable on the basis of density functional theory (DFT) calculations. In addition, for both isothapsadiene and β-isothapsenol, variable-temperature NMR experiments reveal two equilibrium conformers that undergo hindered exchange. The identities of these conformers, which are related by a chair-flip, are confirmed by DFT calculations on their structures, energies, ¹H and ¹³C chemical shifts, and interconversion pathways

Quantification of Toxins in Soapberry (Sapindaceae) Arils: Hypoglycin A and Methylenecyclopropylglycine

Methylenecyclopropylglycine (MCPG) and hypoglycin A (HGA) are naturally occurring amino acids found in some soapberry fruits. Fatalities have been reported worldwide as a result of HGA ingestion, and exposure to MCPG has been implicated recently in the Asian outbreaks of hypoglycemic encephalopathy. In response to an outbreak linked to soapberry ingestion, the authors developed the first method to simultaneously quantify MCPG and HGA in soapberry fruits from 1 to 10 000 ppm of both toxins in dried fruit aril. Further, this is the first report of HGA in litchi, longan, and mamoncillo arils. This method is presented to specifically address the laboratory needs of public-health investigators in the hypoglycemic encephalitis outbreaks linked to soapberry fruit ingestion