A quantum chemical study on the reaction of 1-aryl-1,2-dihydrophosphinine oxides with dimethyl acetylenedicarboxylate

被引：15
作者：
Keglevich, G
Körtvélyesi, T
Ujvári, A
Dudás, E
机构：
[1] Budapest Univ Technol & Econ, Dept Organ Chem Technol, H-1521 Budapest, Hungary
[2] Univ Szeged, Dept Phys Chem, H-6701 Szeged, Hungary
来源：
JOURNAL OF ORGANOMETALLIC CHEMISTRY | 2005年 / 690卷 / 10期
关键词：
P-heterocycles; phosphoranes/ylides; oxaphosphetes; transition states; HOMO-LUMO orbitals;
D O I：
10.1016/j.jorganchem.2004.09.058
中图分类号：
O61 [无机化学];
学科分类号：
070301 ; 081704 ;
摘要：
A beta-oxophosphorane/ylide (2a) and an oxaphosphete (3a), the product and the possible intermediate of an inverse Wittig type reaction of 1-(2,4,6-triisopropylphenyl-)1,2-dihydrophosphinine oxide with dimethyl acetylenedicarboxylate were studied by quantum chemical calculations. The reaction of the title reagents following either a traditional [4 + 2] cycloaddition protocol to afford phosphabicyclo[2.2.2]octadiene 5 or a novel route yielding eventually beta-oxophosphorane/ylide 2 was evaluated by energy calculations. The mechanism for the formation of intermediate 3a(2) was refined by HF/6-31G* transition state calculations. Analysis of the HOMO-LUMO orbitals of the reagents justified the reactivity experienced. (c) 2004 Elsevier B.V. All rights reserved.
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收藏
页码：2497 / 2503
页数：7
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