Abstract
Herein, we report a simplified approach to the synthesis of medium-ring ethers through the electrophilic activation of secondary alcohols with (poly)cationic λ3-iodanes (N-HVI). Excellent levels of selectivity are achieved for C-O bond migration over established α-elimination pathways, enabled by the unique reactivity of a novel 2-OMe-pyridine-ligated N-HVI. The resulting HFIP-acetals are readily derivatized with a range of nucleophiles, providing a versatile functional handle for subsequent manipulations. The utility of this methodology for late-stage natural product derivatization was also demonstrated, providing a new tool for diversity-oriented synthesis and complexity-to-diversity (CTD) efforts. Preliminary mechanistic investigations reveal a strong effect of alcohol conformation on reactive pathway, thus providing a predictive power in the application of this approach to complex molecule synthesis.
References
Apr 15, 2000·Angewandte Chemie·H TohmaY Kita
Apr 14, 2005·Angewandte Chemie·Thomas Wirth
Jun 17, 2005·Organic Letters·Nilesh KumarStuart L Schreiber
Nov 7, 2008·Chemical Reviews·Viktor V Zhdankin, Peter J Stang
Oct 16, 2009·Journal of Medicinal Chemistry·Frank LoveringChristine Humblet
Nov 5, 2011·Science·Eunsung LeeTobias Ritter
Jan 13, 2012·Chemistry : a European Journal·Florian KniepStefan M Huber
Mar 13, 2012·Nature Chemical Biology·Felix KoppDerek S Tan
Oct 16, 2012·Journal of the American Chemical Society·Eunsung LeeTobias Ritter
Nov 15, 2012·Inorganic Chemistry·Thomas P PellJason L Dutton
Feb 21, 2013·Nature Chemistry·Robert W HuigensPaul J Hergenrother
Sep 24, 2015·The Journal of Organic Chemistry·C Wade DowneyAlissa N Nizinski
Feb 11, 2016·Chemical Reviews·Akira Yoshimura, Viktor V Zhdankin
Jul 6, 2016·Journal of the American Chemical Society·Ignacio ColomerRichard G Compton
Aug 25, 2016·Angewandte Chemie·Zheliang YuanSteven H Liang
May 13, 2017·Molecules : a Journal of Synthetic Chemistry and Natural Product Chemistry·Felipe Cesar Sousa E SilvaSarah E Wengryniuk
Citations
Sep 25, 2018·Organic & Biomolecular Chemistry·Harsimran K MinhasMartyna Urbonaite
Nov 24, 2018·Chemical Communications : Chem Comm·Shuai WangJian Xiao
Jul 12, 2019·Angewandte Chemie·Anastassia Matviitsuk, Scott E Denmark
Aug 21, 2019·Angewandte Chemie·Xiao XiaoSarah E Wengryniuk
May 27, 2020·Dalton Transactions : an International Journal of Inorganic Chemistry·Sathsara EgalahewaJason L Dutton
Nov 4, 2020·Chemical Communications : Chem Comm·Beibei ZhangYunfei Du
Dec 10, 2020·Organic & Biomolecular Chemistry·Shuang YangZhenhua Ding
Apr 20, 2021·The Journal of Organic Chemistry·Xiao XiaoSarah E Wengryniuk
Jun 5, 2021·Chemical Science·Anthony F TiernoSarah E Wengryniuk
Jul 8, 2021·Chemical Communications : Chem Comm·Andreas BoelkeBoris J Nachtsheim
Apr 19, 2019·Organic Letters·Wataru YamakoshiKenichi Murai
Dec 17, 2019·Journal of the American Chemical Society·Felipe Cesar Sousa E SilvaSarah E Wengryniuk
Feb 20, 2020·Organic Letters·Ganesh Kumar DhandabaniJeh-Jeng Wang
Jul 17, 2019·Organic Letters·Myriam MikhaelSarah E Wengryniuk
Oct 31, 2019·The Journal of Organic Chemistry·Jiangang TengJiang Cheng
Oct 22, 2021·The Journal of Organic Chemistry·Travis MenardScott E Denmark
Nov 3, 2021·Chemical Communications : Chem Comm·Aseel BakroJason L Dutton