Theoretical study of the concerted and stepwise mechanisms of triazolinedione Diels-Alder reactions

被引:63
作者
Chen, JS [1 ]
Houk, KN [1 ]
Foote, CS [1 ]
机构
[1] Univ Calif Los Angeles, Dept Chem & Biochem, Los Angeles, CA 90095 USA
关键词
D O I
10.1021/ja982050y
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
The Diels-Alder (DA) reactions of triazolinedione (TAD) with s-cis- and s-trans-butadiene have been investigated theoretically with density functional theory; All geometries were fully optimized at the Becke3LYP/6-31G* level. For butadiene, the asynchronous concerted pathway dominates; only stereospecific DA products should be formed. The endo transition structure is 9.7 kcal/mol lower in energy than the exo TS; this exo-lone-pair preference comes from the electrostatic repulsion of the lone pairs on nitrogens with the pi-system of butadiene. The stepwise mechanism leads to an aziridinium imide (AI) intermediate. The stepwise formation of AI intermediates is only 2.9-6.0 kcal/mol higher in energy than the asynchronous concerted mechanism. The AI intermediates can open to form a diradical or zwitterion which can react to yield nonstereospecific Diels-Alder, ene, or solvent-trapping products.
引用
收藏
页码:12303 / 12309
页数:7
相关论文
共 43 条
[1]   [PI-2+PI-2] CYCLOADDITION OF 4-PHENYL-4H-1,2,4-TRIAZOLE-3,5-DIONE AND SINGLET OXYGEN TO HOMOFURAN [J].
ADAM, W ;
GRIESBECK, A ;
KLARNER, FG ;
SCHROER, D .
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION IN ENGLISH, 1986, 25 (11) :989-990
[2]   CYCLOADDITION REACTIONS OF 5H-BENZOCYCLOHEPTENE WITH SINGLET OXYGEN AND WITH 4-PHENYL-1,2,4-TRIAZOLINE-3,5-DIONE, AND THE CHEMISTRY OF THE 5H-BENZOCYCLOHEPTENE ENDOPEROXIDES [J].
ATASOY, B ;
BALCI, M .
TETRAHEDRON, 1986, 42 (05) :1461-1468
[3]   Study of prototypical Diels-Alder reactions by a hybrid density functional Hartree-Fock approach [J].
Barone, V ;
Amaud, R .
CHEMICAL PHYSICS LETTERS, 1996, 251 (5-6) :393-399
[4]   CYCLOADDITION .19. COMPETING CONCERTED AND STEPWISE [2+4] CYCLOADDITION OF DICHLORODIFLUOROETHYLENES TO BUTADIENE AND 2,4-HEXADIENE [J].
BARTLETT, PD ;
MALLET, JJB .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1976, 98 (01) :143-151
[5]   CYCLOADDITION .1. 1,2-ADDITION OF 1,1-DICHLORO-2,2-DIFLUOROETHYLENE TO SOME DIENES [J].
BARTLETT, PD ;
MONTGOMERY, LK ;
SEIDEL, B .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1964, 86 (04) :616-+
[6]   DENSITY-FUNCTIONAL THERMOCHEMISTRY .3. THE ROLE OF EXACT EXCHANGE [J].
BECKE, AD .
JOURNAL OF CHEMICAL PHYSICS, 1993, 98 (07) :5648-5652
[7]  
BENO B, UNPUB
[8]   Synchronous or asynchronous? An ''experimental'' transition state from a direct comparison of experimental and theoretical kinetic isotope effects for a Diels-Alder reaction [J].
Beno, BR ;
Houk, KN ;
Singleton, DA .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1996, 118 (41) :9984-9985
[9]   DETERMINING ATOM-CENTERED MONOPOLES FROM MOLECULAR ELECTROSTATIC POTENTIALS - THE NEED FOR HIGH SAMPLING DENSITY IN FORMAMIDE CONFORMATIONAL-ANALYSIS [J].
BRENEMAN, CM ;
WIBERG, KB .
JOURNAL OF COMPUTATIONAL CHEMISTRY, 1990, 11 (03) :361-373
[10]   The nature of the transition structures of triazolinedione ene reactions [J].
Chen, JS ;
Houk, KN ;
Foote, CS .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1997, 119 (41) :9852-9855