Planar chiral (arene)chromiumcarbonyl-substituted propargyl cations -: A spectroscopic and computational study

被引：4
|
作者：
Netz, Astrid
Drees, Markus
Strassner, Thomas
Mueller, Thomas J. J.
机构：
[1] Abott GmbH & Co KG, ZNS Forsch, Med Chem, D-67061 Ludwigshafen, Germany
[2] Tech Univ Dresden, D-01069 Dresden, Germany
[3] Heidelberg Univ, Inst Organ Chem, D-69120 Heidelberg, Germany
来源：
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY | 2007年 / 2007卷 / 03期
关键词：
alkynes; arene complexes; DFT calculations; cations; chromium; spectroscopy;
D O I：
10.1002/ejoc.200600687
中图分类号：
O62 [有机化学];
学科分类号：
070303 ; 081704 ;
摘要：
Planar chiral (arene)Cr(CO)(3)-substituted propargyl cations can be diastereoselectively generated from propargyl acetates with the use of strong Lewis acids, and they have been structurally characterized by UV/Vis and C-13 NMR spectroscopy. At low temperatures (<-65 degrees C) the s-cis isomer is exclusively obtained as a product of a kinetically controlled ionization. DFT studies on the structure of the propargyl cations and on the C-ipso-C-alpha bond rotation to give the thermodynamically favored s-trans isomer reveal that the substitution pattern at the gamma-propargyl position has a stronger impact on the height of the rotational barrier than the substituent on the complexed aryl ring. ((c) Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007).
引用
收藏
页码：540 / 547
页数：8
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