The importance of asking “how and why?” in natural product structure elucidation

Abstract

This review highlights why careful consideration of the biosynthetic origin (the how) and the biological function (the why) of a natural product can be so useful during the determination of its structure. Recent examples of structural reassignments inspired by biosynthetic and functional insights will be presented. This review will demonstrate the importance of viewing the origin, structure and function of a natural product as intertwined threads of a single story, best viewed as a whole rather than as discrete topics.

Visible‐Light Photoredox Catalysis Enables the Biomimetic Synthesis of Nyingchinoids A, B, and D, and Rasumatranin D

“…The coupling constant of 14 Hz between H‐3 and H‐11, and the absence of an nOe interaction, indicates a trans relationship at this ring junction of 16 . Furthermore, the co‐isolation of the cyclobutane natural product 17 alongside rasumatranin D suggested a common chromene biosynthetic precursor with the same aromatic substitution pattern as the nyingchinoids …”

Reassignments and Corroborations of Oxo‐Bridged Natural Products Directed by OSE and DU8+ NMR Computation

“…Forthe Cytisus monoterpene 28,abiosynthetic analysis [35] suggested ap ossible origin in chakyunglupulin A( 37)o rB (38), [36] via ac yclodehydration step ( Figure 6). Therefore oxetane 39 was postulated as an alternative structure, however, the predicted NMR did not match with experiment.…”

Reassignments and Corroborations of Oxo‐Bridged Natural Products Directed by OSE and DU8+ NMR Computation

“…For the Cytisus monoterpene 28 , a biosynthetic analysis suggested a possible origin in chakyunglupulin A ( 37 ) or B ( 38 ), via a cyclodehydration step (Figure ). Therefore oxetane 39 was postulated as an alternative structure, however, the predicted NMR did not match with experiment.…”