NMR- and MS-guided metabolomic mining for new
phytoconstituents from a widely used dietary supplement, <i>Rhodiola rosea</i>, yielded two new (+)-myrtenol glycosides, <b>1</b> and <b>2</b>, and two new cuminol glycosides (<b>3</b> and <b>4</b>), along with
three known analogues (<b>5</b>–<b>7</b>). The structures of the new compounds
were determined by extensive spectroscopic analysis. Quantum Mechanics-driven <sup>1</sup>H
iterative Full Spin Analysis (QM-HiFSA) decoded the spatial arrangement of the
methyl groups in <b>1</b> and <b>2</b>, as well as other features not recognizable
by conventional methods, including higher order spin-coupling effects. The
application of QM-HiFSA will provide a definitive reference point for future
phytochemical and biological studies of <i>R.
rosea</i> as a resilience botanical. Application of a new NMR data analysis software package, CT,
for QM-based iteration of NMR spectra is also discussed.