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Conformational Bias by a Removable Silyl Group: Construction of Bicyclo[ n .3.1]alkenes by Ring Closing Metathesis
Author(s) -
Lin Minggui,
Cai PeiJun,
Zeng Zhixiong,
Lin Na,
Shen Yang,
Tang Bin,
Li Fan,
Chen Chen,
Yu ZhiXiang,
Zhang Yandong
Publication year - 2018
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201705275
Subject(s) - silylation , bicyclic molecule , chemistry , conformational isomerism , metathesis , ring closing metathesis , ring (chemistry) , stereochemistry , salt metathesis reaction , molecule , group (periodic table) , organic chemistry , catalysis , polymer , polymerization
Herein, we report a novel strategy based on a conformationally controlled RCM by a removable silyl group, which allows the facile synthesis of various bicyclo[ n .3.1]alkenes, especially a set of highly strained bicyclo[5.3.1]alkenes. Further derivatizations of the silyl group and the resultant double bond of bicyclo[5.3.1]undecene 2 f enabled a concise synthesis of A‐B‐C ring skeleton of taxol. Density functional theory (DFT) calculations suggest that the introduction of a bulky silyl group at C‐5 position of the 1,3‐dialkenylcyclohexanol substrates dramatically lowers the energy bias gap between diaxial conformers (to RCM) and diequatorial conformers (to cross metathesis), thereby favoring the expected RCM reaction to give the challenging bridged molecules.