Generation and Reactivity of Aza-Oxyallyl Cationic Intermediates: Aza-[4+3] Cycloaddition Reactions for Heterocycle Synthesis

被引：176
作者：
Jeffrey, Christopher S. [1 ]
Barnes, Korry L. [1 ]
Eickhoff, John A. [1 ]
Carson, Christopher R. [1 ]
机构：
[1] Univ Nevada, Dept Chem, Reno, NV 89557 USA
来源：
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY | 2011年 / 133卷 / 20期
关键词：
QUANTUM-CHEMICAL CHARACTERIZATION; INTRAMOLECULAR 4+3 CYCLOADDITIONS; ALLYL CATIONS; STEREOSELECTIVITY; IONS; FURAN; DFT; DIASTEREOSELECTIVITY; CYCLOPENTADIENE; TRIETHYLAMINE;
D O I：
10.1021/ja201901d
中图分类号：
O6 [化学];
学科分类号：
0703 ;
摘要：
Aza-[4 + 3] cycloadditions of putative azaoxyallyl cationic intermediates and cyclic dienes are reported. The intermediate is generated by the dehydrohalogenation of alpha-haloamides. The reaction is general to a variety of alpha-haloamides and is diastereoselective. Computational and experimental data suggest that an N-alkoxy substituent stabilizes the aza-oxyallyl cationic intermediate.
引用
收藏
页码：7688 / 7691
页数：4
相关论文
共 66 条
[1]   An unexpected reversal of diastereoselectivity in the [4+3]-cycloaddition reaction of nitrogen-stabilized oxyallyl cations with methyl 2-furoate [J].
Antoline, Jennifer E. ;
Hsung, Richard P. .
SYNLETT, 2008, (05) :739-744
[2]   Highly stereoselective [4+3] cycloadditions of nitrogen-stabilized oxyallyl cations with pyrroles. An approach to parvineostemonine [J].
Antoline, Jennifer E. ;
Hsung, Richard P. ;
Huang, Jian ;
Song, Zhenlei ;
Li, Gang .
ORGANIC LETTERS, 2007, 9 (07) :1275-1278
[3]   Bicyclo[3.2.1]octanone catalysts for asymmetric alkene epoxidation: the effect of disubstitution [J].
Armstrong, Alan ;
Dominguez-Fernandez, Belen ;
Tsuchiya, Tomoki .
TETRAHEDRON, 2006, 62 (28) :6614-6620
[4]   Understanding the nature of the molecular mechanisms associated with the competitive Lewis acid catalyzed [4+2] and [4+3] cycloadditions between arylidenoxazolone systems and cyclopentadiene:: A DFT analysis [J].
Arnó, M ;
Picher, MT ;
Domingo, LR ;
Andrés, J .
CHEMISTRY-A EUROPEAN JOURNAL, 2004, 10 (19) :4742-4749
[5]   Stereoselective preparation of (Z)-2-(trialkylsilyloxy)-2-alkenals by retrocycloaddition reactions of 4H-4-alkyl-5-(trialkylsilyloxy)-1,3-dioxins.: Useful reactants for Lewis acid catalyzed [4+3] cyclizations [J].
Aungst, RA ;
Funk, RL .
ORGANIC LETTERS, 2001, 3 (22) :3553-3555
[6]   Quantum calculation of molecular energies and energy gradients in solution by a conductor solvent model [J].
Barone, V ;
Cossi, M .
JOURNAL OF PHYSICAL CHEMISTRY A, 1998, 102 (11) :1995-2001
[7]  
Barone V, 1998, J COMPUT CHEM, V19, P404, DOI 10.1002/(SICI)1096-987X(199803)19:4<404::AID-JCC3>3.0.CO
[8]  
2-W
[9]  
Cha JK, 1998, CURR ORG CHEM, V2, P217
[10]   Time-resolved IR detection and study of an iminooxirane intermediate [J].
Cohen, AD ;
Showalter, BM ;
Toscano, JP .
ORGANIC LETTERS, 2004, 6 (03) :401-403
1234567