New structurally interesting cyclopropane derivatives. A world of wonders and surprises

被引:22
作者
de Meijere, A
Kozhushkov, SI
Fokin, AA
Emme, I
Redlich, S
Schreiner, PR
机构
[1] Univ Gottingen, Inst Organ Chem, D-37077 Gottingen, Germany
[2] Univ Giessen, Inst Organ Chem, D-35392 Giessen, Germany
关键词
D O I
10.1351/pac200375050549
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
The structurally intriguing [4]- and [5]triangulanes have been prepared in enantiomerically pure form. Their surprisingly high specific rotations are well reproduced by DFT/SCI computations and stem from the fact that these hydrocarbons essentially are sigma-helicenes (i.e., rigidly held helical arrangements of sigma-bonds). Some light is shed on the properties of radical cations derived from [3]- and [4]rotanes. While the former adopts C-s or C-2v symmetry, the latter retains the D-4h symmetry of the neutral hydrocarbon, according to high-level computations. Experimental and computational evidence is also presented that the anti-aromatic cyclopentadienyl cation is stabilized as a singlet ground state by five cyclopropyl substituents. Yet, the three cyclopropyl groups in tricyclopropylamine do not favor the formation of its radical cation, because they are not in the proper orientation. When this amine radical cation is generated by cobalt gamma-irradiation in a Freon matrix, evidence for a significant conformational change is obtained by EPR spectroscopy. Finally, the conformational dynamics of the newly prepared crowded molecules tetracyclopropyl- and tetraisopropyl-methane are discussed.
引用
收藏
页码:549 / 562
页数:14
相关论文
共 78 条
[1]   Conformational dynamics of tetraisopropylmethane and of tetracyclopropylmethane [J].
Anderson, JE ;
de Meijere, A ;
Kozhushkov, SI ;
Lunazzi, L ;
Mazzanti, A .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2002, 124 (23) :6706-6713
[2]  
[Anonymous], ANGEW CHEM
[3]  
[Anonymous], 1991, ANGEW CHEM, V103, P193
[4]   Synthesis and characterization of coronanes: Multicyclopropane-fused macrocyclic arrays [J].
Barrett, AGM ;
Hamprecht, D ;
James, RA ;
Ohkubo, M ;
Procopiou, PA ;
Toledo, MA ;
White, AJP ;
Williams, DJ .
JOURNAL OF ORGANIC CHEMISTRY, 2001, 66 (07) :2187-2196
[5]   STRUCTURES OF STERICALLY OVERCROWDED AND CHARGE-PERTURBED MOLECULES .5. GAS-PHASE STRUCTURES OF FLATTENED AMINES .4. TRIISOPROPYLAMINE - A STERICALLY OVERCROWDED MOLECULE WITH A FLATTENED NC3 PYRAMID AND A P-TYPE NITROGEN ELECTRON PAIR [J].
BOCK, H ;
GOEBEL, I ;
HAVLAS, Z ;
LIEDLE, S ;
OBERHAMMER, H .
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION IN ENGLISH, 1991, 30 (02) :187-190
[6]   Non-planar structures of Et3N and Pri3 N:: a contradiction between the x-ray, and NMR and electron diffraction data for Pri3N [J].
Boese, R ;
Bläser, D ;
Antipin, MY ;
Chaplinski, V ;
de Meijere, A .
CHEMICAL COMMUNICATIONS, 1998, (07) :781-782
[7]   ELECTROCHEMICAL DETERMINATION OF PKR+ FOR SOME ANTIAROMATIC CYCLOPENTADIENYL CATIONS [J].
BRESLOW, R ;
MAZUR, S .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1973, 95 (02) :584-585
[8]   PENTACHLOROCYCLOPENTADIENYL CATION GROUND-STATE TRIPLET [J].
BRESLOW, R ;
HILL, R ;
WASSERMAN, E .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1964, 86 (23) :5349-&
[9]   ABOUT SUBSTITUTED PENTA-PHENYL-CYCLO-PENTA-DIENYL-COMPOUNDS AND TATRA-CYCLONES .4. UNSYMMETRICAL P-METHYL-AND P-PHENYL-SUBSTITUTED PENTA-PHENY-CYCLO-PENTA-DIENYL-KATIONS AND-RADICALS [J].
BROSER, W ;
SIEGLE, P ;
KURRECK, H .
CHEMISCHE BERICHTE-RECUEIL, 1968, 101 (01) :69-&
[10]   UBER SUBSTITUIERTE PENTAPHENYL-CYCLOPENTADIENYL-VERBINDUNGEN UND TETRACYCLONE .3. SYMMETRISCCHE CYCLOPENTADIENYL-KATIONEN MIT NACHWEISBAREN TRIPLETTZUSTANDEN [J].
BROSER, W ;
KURRECK, H ;
SIEGLE, P .
CHEMISCHE BERICHTE-RECUEIL, 1967, 100 (03) :788-&