Catalytic Synthesis of Saturated Oxygen Heterocycles by Hydrofunctionalization of Unactivated Olefins: Unprotected and Protected Strategies

A mild, general, and functional group tolerant intramolecular hydroalkoxylation and hydroacyloxylation of unactivated olefins using a Co­(salen) complex, an N-fluoropyridinium salt, and a disiloxane reagent is described. This reaction was carried out at room temperature and afforded five- and six-me...

Full description

Saved in:
Bibliographic Details
Published in:Journal of the American Chemical Society 2016-08, Vol.138 (33), p.10597-10604
Main Authors: Shigehisa, Hiroki, Hayashi, Miki, Ohkawa, Haruna, Suzuki, Tsuyoshi, Okayasu, Hiroki, Mukai, Mayumi, Yamazaki, Ayaka, Kawai, Ryohei, Kikuchi, Harue, Satoh, Yui, Fukuyama, Akane, Hiroya, Kou
Format: Article
Language:English
Citations: Items that this one cites
Items that cite this one
Online Access:Get full text
Tags: Add Tag
No Tags, Be the first to tag this record!
Description
Summary:A mild, general, and functional group tolerant intramolecular hydroalkoxylation and hydroacyloxylation of unactivated olefins using a Co­(salen) complex, an N-fluoropyridinium salt, and a disiloxane reagent is described. This reaction was carried out at room temperature and afforded five- and six-membered oxygen heterocyclic compounds, such as cyclic ethers and lactones. The Co complex was optimized for previously rare medium ring formation by hydrofunctionalization of unactivated olefins. The powerful Co catalyst system also enables the deprotective hydroalkoxylation of O-protected alkenyl alcohol and hydroacyloxylation of alkenyl ester to afford cyclic ethers and lactones directly. The substrate scope and mechanistic proof of deprotection were investigated. The experimental evidence supports the concerted transition state of the bond-forming step involving a cationic Co complex.
ISSN:0002-7863
1520-5126
DOI:10.1021/jacs.6b05720