Facile 1,3- and 1,5-chlorine migration

Koch R., Wong M.W. and Wentrup C. (1996) Facile 1,3- and 1,5-chlorine migration. Journal of Organic Chemistry, 61 20: 6809-6813. doi:10.1021/jo9740002


Author Koch R.
Wong M.W.
Wentrup C.
Title Facile 1,3- and 1,5-chlorine migration
Journal name Journal of Organic Chemistry   Check publisher's open access policy
ISSN 0022-3263
Publication date 1996-10-04
Year available 1997
Sub-type Article (original research)
DOI 10.1021/jo9740002
Open Access Status Not yet assessed
Volume 61
Issue 20
Start page 6809
End page 6813
Total pages 5
Place of publication WASHINGTON
Publisher AMER CHEMICAL SOC
Language eng
Subject 1605 Policy and Administration
Abstract High-level ab initio molecular orbital calculations, using the GB(MP2,SVP) theory (and semiempirical methods) have been used to examine several 1,3- and 1,5-chlorine migrations. It is found that the interaction of chlorine lone pair electrons with a low-lying LUMO accelerates the C1 shift dramatically (lone pair-LUMO-mediated pericyclic reaction) The activation barriers for the 1,3-migration in chloro oxo ketene 1 (Cl(C=O)CH=C=O) and the 1,5-migration in (2-(chlorocarbonyl)-vinyl)ketene 2 (Cl(C=O)CH=CHCH=C=O) are only 53 and 61 kJ mol(-1), respectively, compared to the 216 and 173 kJ mol(-1) barriers for the corresponding unassisted 1,3- and 1,5-sigmatropic shifts of C1 in 8-chloro-1-propene and 5-chloro-1,3-pentadiene. The transition structures for 1 and 2 reveal that migration of the chlorine atoms takes place in the molecular planes. The 1,5-chlorine shift in 6-chlorocyclohexa-2,4-dienone (3) has a significantly higher barrier due to a lack of appropriate orbital interaction. The related 1.3-shift in the (chlorocarbonyl)imine-alpha-chloro isocyanate system is also dramatically accelerated compared with conventional pericyclic 1,3-Cl migration.
Keyword 1,5-Sigmatropic Shifts
Cyclopentadiene Ring
Rearrangement
Imidoylketene
Chlorination
Formylketene
Vinylketene
Parameters
Q-Index Code C1
Q-Index Status Provisional Code
Institutional Status Unknown

Document type: Journal Article
Sub-type: Article (original research)
Collection: Scopus Import - Archived
 
Versions
Version Filter Type
Citation counts: TR Web of Science Citation Count  Cited 2 times in Thomson Reuters Web of Science Article | Citations
Scopus Citation Count Cited 46 times in Scopus Article | Citations
Google Scholar Search Google Scholar
Created: Tue, 05 Jul 2016, 15:39:36 EST by System User