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ID 20645
file
creator
Jiang, Xin-Dong
Kakuda, Ken-ichiro
Matsukawa, Shiro
Yamamichi, Hideaki
subject
hypervalent compounds
isomerization
spiro compounds
steric hindrance
X-ray diffraction
NDC
Chemistry
abstract
1,1,1,2,2,4,4,5,5,5-Decafluoro-3-phenyl-3-pentanol (13) was prepared via the Cannizzaro-type disproportionation reaction, and dimetallated 13 (i.e., 15) was used as a bidentate ligand, which was bulkier than the Martin ligand (1,1,1,3,3,3-hexafluoro-2-phenyl-2-propanol). P-H spirophosphorane (16) was synthesized utilizing the new bidentate ligand, and the structure of 16 was essentially the same as that of the P-H phosphorane with the Martin ligands (1b). Phosphoranes which exhibit reversed apicophilicity (9: O-equatorial) were also synthesized and could be converted to the corresponding stable stereoisomers (10: O-apical). The crystal structures of O-equatorial phosphoranes (9) and those of O-apical isomers (10) were slightly affected by the steric repulsion of pentafluoroethyl groups. Kinetic measurements revealed that the stereomutation of O-equatorial methylphosphorane (9a) to the O-apical isomer (10a) was slowed. The activation enthalpy for the stereomutation of 9a→10a (24.4 kcal mol–1) was higher than that of the phosphorane bearing the Martin ligands (3a→4a: 19.3 kcal mol–1) by 5.1 kcal mol–1.
journal title
Chemistry - An Asian Journal
volume
Volume 2
issue
Issue 2
start page
314
end page
323
date of issued
2007
publisher
Wiley-VCH Verlag GmbH
issn
1861-4728
ncid
publisher doi
language
eng
nii type
Journal Article
HU type
Journal Articles
DCMI type
text
format
application/pdf
text version
author
rights
Copyright (c) 2007 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
relation url
department
Graduate School of Science