Journal of the Chemical Society. Perkin transactions I p. 315 - 329 (1984)
Update date:2022-08-16
Topics:
Benner, Jill P.
Gill, G. Bryon
Parrott, Stephen J.
Wallace, Brian
Begley, Michael J.
The Lewis acid catalysed ene additions of chloral and bromal to alkenes are completely regiospecific, moderately regioselective, and often highly stereoselective.Diastereoselectivity in the addition to (-)-β-pinene was a function of the Lewis acid, and with TiCl4 essentially quantitative asymmetric induction was observed.The stereochemical phenomena are explained satisfactory by assuming the active enophiles possess transoid structures such as (1), that a concerted or rapid stepwise mechanism operates, and that product formation occurs predominantly through the least hindered encounter complex of the olefin and (1).In the case of 2-methylbut-2-ene, however, there is some evidence for an additional stereoelectronic contribution, the 'cis-effect'.Stereochemical assignements are supported by X-ray structural data.Ketones, hydrohalogenated ene adducts, or rearrangement products are formed (mainly in the addition to olefins of moderate reactivity) indicating the participation of Friedel-Crafts type dipolar intermediates.The ene adducts themselves could be formed via dipolar intermediates or in competing 'concerted' reactions; the stepwise mechanism must operate in some reactions because of the observation of Wagner-Meerwein rearrangements.Olefin reactivity over the series, measured by the competitive technique, towards chloral-AlCl3 showed a ca. 900-fold variation in rate; 'ene' reactivity decreases more steeply.
View MoreHuangshi Meifeng Chemical Co.,ltd.
Contact:+86-714-6516706
Address:1941-4-3#,Hubin Avenue,Huangshi,Hubei,China
Suqian Ruixing Chemical Co., Ltd.
Contact:+86-527-80805666（总机）;84836008(销售)
Address:3 Jingsilu, Zone north, Hubin Xincheng Development Park, Suqian, China
Contact:+86-29-88710656
Address:South Tai bai Road, High Tech Development Zone, Xi'an China
Hubei Onward Bio-Development Co., Ltd.
Contact:+86-718-8417012
Address:No.517,Shizhou Avenue,Enshi City,Hubei Province,China,445002
website:http://www.sigmaaldrich.com
Contact:800 558-9160
Address:Industriestrasse 25CH-9471 Buchs SGSwitzerland
Doi:10.1021/jo00882a035
(1976)Doi:10.1002/adfm.202100877
(2021)Doi:10.1039/c0cc02823a
(2010)Doi:10.1080/00397910600770839
(2006)Doi:10.1016/S0040-4020(01)87685-7
(1987)Doi:10.1021/acs.jmedchem.7b00083
(2017)
