STEREOCHEMISTRY AND CHIROPTICAL PROPERTIES OF THE NONPLANAR NITROSAMINE GROUP IN N-NITROSOAZIRIDINES

被引:24
作者
SHUSTOV, GV
KACHANOV, AV
KADORKINA, GK
KOSTYANOVSKY, RG
RAUK, A
机构
[1] RUSSIAN ACAD SCI,INST CHEM PHYS,MOSCOW,USSR
[2] UNIV CALGARY,DEPT CHEM,CALGARY T2N 1N4,ALBERTA,CANADA
关键词
D O I
10.1021/ja00047a041
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
The stereochemistry and the chiroptical properties of the nonplanar nitrosamine group were investigated by means of nonempirical quantum chemical calculations on 1-nitrosoaziridine (1), (2R)-2-methyl-1-nitrosoaziridine (2), and (2S,3S)-2,3-dimethyl-1-nitrosoaziridine (3), and by experimental measurement of the CD spectra of compounds 2, 3, (2S)-2-carbomethoxy-1-nitrosoaziridine (4), and (2S,3S)-2,3-bis(isopropoxycarbonyl)-1-nitrosoaziridine (5). The first electronic transition which occurs in the region 350-500 nm is assigned as n(O) --> pi*, and is shown to be very similar to that found for N-acylaziridine and gauche-cyclopropyl ketones. For all three systems, the sign of the longest wavelength Cotton effect (CE) follows a "spiral rule" or, equivalently, a 'reverse octant rule". The second transition which has an oppositely signed and stronger CE is assigned as a pi --> pi* transition of the inherently chiral NNO chromopore. The presence of the ester functionality (compounds 4 and 5) results in a reversal of the CE signs of both the n(O) --> pi* and pi --> pi* transitions in the nonplanar nitrosamine chromophore, that is, a reversal of the normal sector-related behavior of this chromophore.
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页码:8257 / 8262
页数:6
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