Total Synthesis of (+)-Antrocin and Its Diastereomer and Clarification of the Absolute Stereochemistry of (−)-Antrocin

Autor:	Ming-Der Su, Wei-Sheng Chang, Jia-Syun Lu, Kai-Hsiang Liang, Te-Fang Yang, Sheng-Han Huang
Rok vydání:	2017
Předmět:	010405 organic chemistry Stereochemistry Organic Chemistry Diastereomer Cyclohexanol Cyclohexanone Total synthesis 010402 general chemistry 01 natural sciences Transition state 0104 chemical sciences chemistry.chemical_compound chemistry Magnesium bromide Stereoselectivity Derivative (chemistry)
Zdroj:	The Journal of Organic Chemistry. 82:9576-9584
ISSN:	1520-6904 0022-3263
DOI:	10.1021/acs.joc.7b01600
Popis:	Using 2,2-dimethyl cyclohexanone as the starting compound, (+)-antrocin and its diastereomer have been synthesized. The absolute stereochemistry of (-)-antrocin, a natural sesqui-terpenoid and an antagonist in some types of cancer cells, was clarified using the character data of (+)-antrocin. The synthetic procedure involved two key steps: (1) the reaction of vinyl magnesium bromide with 2,2-dimethyl-6-t-butyl-dimethyl-silyoxy-methyl-1-cyclo-hexanone to give a vinyl cyclohexanol derivative and (2) a highly stereoselective intramolecular Diels-Alder (IMDA) reaction of the camphanate-containing triene intermediate. The relative energy levels of the possible transition states of the IMDA reaction of the camphanate-containing triene were obtained from density functional theory calculations, proving the stereospecific formation of the target molecule.
Databáze:	OpenAIRE
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