Open AccessTotal Synthesis of Penicibilaenes via C–C Activation-Enabled Skeleton Deconstruction and Desaturation Relay-Mediated C–H Functionalization
Author(s) -
Yibin Xue,
Guangbin Dong
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.1c04335
Subject(s) - chemistry , surface modification , relay , skeleton (computer programming) , deconstruction (building) , stereochemistry , ecology , power (physics) , physics , quantum mechanics , computer science , biology , programming language
Herein, we describe the first total synthesis of sesquiterpene penicibilaenes A and B through a "C-C/C-H" approach. In the "C-C" stage, the Rh-catalyzed "cut-and-sew" transformation between trisubstituted alkene and cyclobutanone has been employed to construct the unique tricyclo[6.3.1.0 1,5 ]dodecane skeleton and the all-carbon quaternary center. Critical linker and Lewis acid effects have been identified for the C-C activation process. In the "C-H" stage, a desaturation relay-based strategy involving consecutive ketone α,β-dehydrogenation and β-functionalization has been adopted to introduce the 1,3,5-triad stereocenters to the core. The synthesis of penicibilaenes A and B has been completed in 13 and 14 steps, respectively, in the longest linear sequence.