AUTHOR=Tan Jiashen , Zhu Weiqin , Xu Weiping , Jing Yaru , Ke Zhuofeng , Liu Yan , Maruoka Keiji 

TITLE=Hypervalent Iodine-Mediated Diastereoselective α-Acetoxylation of Cyclic Ketones

JOURNAL=Frontiers in Chemistry

VOLUME=Volume 8 - 2020

YEAR=2020

URL=https://www.frontiersin.org/journals/chemistry/articles/10.3389/fchem.2020.00467

DOI=10.3389/fchem.2020.00467

ISSN=2296-2646

ABSTRACT=A binary hybrid system comprising hypervalent iodine(III) reagent and BF3•OEt2 Lewis acid was found to be effective for the diastereoselective α-acetoxylation of cyclic ketones. In this hybrid system, BF3•OEt2 Lewis acid allowed the activation of hypervalent iodine (III) reagent and cyclic ketones for the smooth alpha-acetoxylation reaction, achieving high diastereoselectivity. This hypervalent iodine mediated α-acetoxylation of cyclic ketone reaction plausibly undergoes an SN2 substitution mechanism via α-C-bound hypervalent iodine intermediate. The diastereoselectivity of the reaction is mainly originated from thermodynamic control.