Experimental and Calculated CPL Spectra and Related Spectroscopic Data of Camphor and Other Simple Chiral Bicyclic Ketones
Experimental and Calculated CPL Spectra and Related Spectroscopic Data of Camphor and Other Simple Chiral Bicyclic Ketones
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DOI：
10.1002/chir.22176
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发表时间：
2013-10-01
期刊：
影响因子：
2
通讯作者：
Lightner, David A.
中科院分区：
文献类型：
--
作者：
Longhi, Giovanna;Castiglioni, Ettore;Lightner, David A.
记录了一组四种相关的[2.2.1]双环化合物（（1 S，4S）-和（1 R，4 R）-1，7，7-三甲基双环[2.2.1]庚-2-酮，即（1 S）-和（1 R）-樟脑（1），（1 S，4 R）-4，7，7-三甲基双环[2.2.1]庚-5-烯-2-酮，（1 S）-脱氢-表樟脑（2），（1 S，4S）-1，7，7-三甲基双环[2.2.1]庚烷-2，5-二酮，（1 S）-5-氧代樟脑（3），（1 S，4 R）-和（1 R，4S）-1，7，7-三甲基双环[2.2.1]庚烷-2，3-二酮，（1 S）-和（1 R）-蒽醌（4））和一组三种相关的[2.2.2]双环化合物（1 S，4S）-双环[2.2.2]辛-2，5-二酮（饱和二酮（5）），（1 R，4 R）-双环[2.2.2]辛-7-烯-2，5-二酮（不饱和二酮（6）），（（1 S，4S）-双环[2.2.2]辛-7-烯-5（S）-醇-2-酮（我们称之为不饱和羟基-酮（7））。对于后三种化合物也中红外振动圆二色性（VCD）光谱进行了记录和介绍。含时密度泛函（TD-DFT）计算提供了一个令人满意的解释吸收和发射手性光谱，并允许洞察基态和激发态的电子性质。我们讨论了八分圆规则或其他近似模型的适用性，以合理化所观察到的CPL的符号。手性25：589-599，2013。(c)2013 Wiley Periodicals，Inc.
UV, circular dichroism (CD), fluorescence and circularly polarized luminescence (CPL) spectra were recorded for a set of four related [2.2.1] bicyclic compounds ((1S,4S)-and (1R,4R)-1,7,7-trimethylbicyclo[2.2.1]heptan-2-one, namely (1S)- and (1R)-camphor (1), (1S,4R)-4,7,7-trimethylbicyclo[2.2.1]hept-5-en-2-one, (1S)-dehydro-epicamphor (2), (1S,4S)-1,7,7-trimethylbicyclo[2.2.1]heptane-2,5-dione, (1S)-5-oxocamphor (3), (1S,4R)- and (1R,4S)-1,7,7-trimethylbicyclo[2.2.1]heptane-2,3-dione, (1S)- and (1R)-camphorquinone (4)) and a set of three related [2.2.2] bicyclic compounds (1S,4S)-bicyclo[2.2.2]octan-2,5-dione (saturated diketone (5)), (1R,4R)-bicyclo[2.2.2]oct-7-en-2,5-dione (unsaturated diketone (6)), ((1S,4S)-bicyclo[2.2.2]oct-7-en-5(S)-ol-2-one (which we refer to as unsaturated hydroxy-ketone (7)). For the latter three compounds also mid-IR vibrational circular dichroism (VCD) spectra were recorded and are presented. Time-Dependent Density Functional (TD-DFT) calculations provide a satisfactory interpretation of both absorption and emission chiroptical spectra and permit insight into ground and excited state electronic properties. We discuss the applicability of the octant rule or of other approximated models to rationalize the observed sign of the CPL. Chirality 25:589-599, 2013. (c) 2013 Wiley Periodicals, Inc.