A detailed investigation was carried out to understand how the variations in configurations of the spiroannulated 6-6-6-5-5 pentacyclic diastereoisomers, the key intermediates for the synthesis of two C30 terpene quinonemethides and their stereoisomers, impact the reactivity of cyclopropanation. The configurations at C9, C8, and C14 for all four pentacyclic diastereoisomers involved in the diastereoisomeric mixture were determined through a combination of suitable chemical derivatization and multiple NMR spectroscopic analyses. Based on the defined configuration, the 3D structures of these diastereoisomers were optimized by DFT calculation. These investigations provide reasonable supports, mainly from the steric considerations, for understanding why different diastereoisomers exhibit markedly different reactivity and regio- and stereo-selectivity for cyclopropanation. In addition, the mechanism for the construction of the spiroannulated 6-6-6-5-5 pentacyclic scaffold via intramolecular Michael/aldol cascade was also investigated by deuterium labeling experiments.
张元贺
,
沈运杰
,
谈东兴
,
韩福社
. Study on the Cyclopropanation Reactivity and Selectivity of Spiroannulated Pentacyclic Diastereoisomers toward Synthesizing Cryptoquinonemethides[J]. Chinese Journal of Organic Chemistry, 0
: 0
.
DOI: 10.6023/cjoc202508010
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