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Visible‐Light Photoredox Catalysis Enables the Biomimetic Synthesis of Nyingchinoids A, B, and D, and Rasumatranin D
Author(s) -
Hart Jacob D.,
Burchill Laura,
Day Aaron J.,
Newton Christopher G.,
Sumby Christopher J.,
Huang David M.,
George Jonathan H.
Publication year - 2019
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.201814089
Subject(s) - cycloaddition , cyclobutane , chemistry , photoredox catalysis , photochemistry , catalysis , stereochemistry , organic chemistry , ring (chemistry) , photocatalysis
The total synthesis of nyingchinoids A and B has been achieved through successive rearrangements of a 1,2‐dioxane intermediate that was assembled using a visible‐light photoredox‐catalysed aerobic [2+2+2] cycloaddition. Nyingchinoid D was synthesised with a competing [2+2] cycloaddition. Based on NMR data and biosynthetic speculation, we proposed a structure revision of the related natural product rasumatranin D, which was confirmed through total synthesis. Under photoredox conditions, we observed the conversion of a cyclobutane into a 1,2‐dioxane through retro‐[2+2] cycloaddition followed by aerobic [2+2+2] cycloaddition.