Open AccessRearrangements of the Chrysanthenol Core: Application to a Formal Synthesis of Xishacorene B
Author(s) -
Kerry E. Jones,
Bohyun Park,
Nicolle A. Doering,
MuHyun Baik,
Richmond Sarpong
Publication year - 2021
Publication title -
journal of the american chemical society
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 7.115
H-Index - 612
eISSN - 1520-5126
pISSN - 0002-7863
DOI - 10.1021/jacs.1c10804
Subject(s) - chemistry , reactivity (psychology) , bicyclic molecule , formal synthesis , natural product , core (optical fiber) , stereochemistry , substrate (aquarium) , combinatorial chemistry , cope rearrangement , computer science , medicine , telecommunications , oceanography , alternative medicine , pathology , geology
Reported here are substrate-dictated rearrangements of chrysanthenol derivatives prepared from verbenone to access complex bicyclic frameworks. These rearrangements set the stage for a 10-step formal synthesis of the natural product xishacorene B. Key steps include an anionic allenol oxy-Cope rearrangement and a Suárez directed C-H functionalization. The success of this work was guided by extensive computational calculations which provided invaluable insight into the reactivity of the chrysanthenol-derived systems, especially in the key oxy-Cope rearrangement.