Pressure and temperature control of product chirality in asymmetric photochemistry. Enantiodifferentiating photoisomerization of cyclooctene sensitized by chiral benzenepolycarboxylates

被引:88
作者
Inoue, Y
Matsushima, E
Wada, T
机构
[1] Osaka Univ, Fac Engn, Dept Mol Chem, Suita, Osaka 5650871, Japan
[2] JST, ERATO, Inoue Photochirogenesis Project, Toyonaka, Osaka 5650085, Japan
关键词
D O I
10.1021/ja981929a
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
Pressure effects upon asymmetric photosensitization have been investigated for the first time in the enantiodifferentiating Z-E photoisomerization of cyclooctene (1), sensitized by chiral aromatic esters (2-7). The product's enantiomeric excess (ee) and E/Z ratio were critical functions of the applied pressure, exhibiting an unprecedented switching of the product chirality. Depending upon the chiral sensitizer employed, the differential activation volume (Delta Delta V double dagger) varies widely from -3.7 to +5.6 cm(3) mol(-1), which is unexpectedly large for an enantiodifferentiation in the excited state. However, the Delta Delta V double dagger values obtained do not correlate with the differential activation enthalpy (Delta Delta H double dagger) or entropy (Delta Delta S double dagger) obtained from temperature-dependence studies, indicating that pressure and temperature function as independent perturbants for the photoenantio-differentiation process. Further investigations on the pressure dependence of ee at low temperatures enable us to construct the first three-dimensional diagram that correlates the product's ee with pressure and temperature changes. The combined effects of temperature and pressure provide us with a versatile tool for the multidimensional control of asymmetric photochemical reactions, in which we can switch and/or enhance the product chirality at more readily accessible temperatures and pressures, without using antipodal sensitizers;
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页码:10687 / 10696
页数:10
相关论文
共 60 条
[1]  
[Anonymous], 1997, ADV SUPR CH
[2]   2-STEP MECHANISM IN SINGLE-STEP ISOMERIZATIONS - KINETICS IN HIGHLY VISCOUS-LIQUID PHASE [J].
ASANO, T ;
FURUTA, H ;
SUMI, H .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1994, 116 (13) :5545-5550
[3]   ACTIVATION AND REACTION VOLUMES IN SOLUTION [J].
ASANO, T ;
LENOBLE, J .
CHEMICAL REVIEWS, 1978, 78 (04) :407-489
[4]   EXPERIMENTAL VOLUMETRIC PROPERTIES OF LIQUID NORMAL-ALKANES AND THEIR BINARY-MIXTURES [J].
BLINOWSKA, A ;
BROSTOW, W .
JOURNAL OF CHEMICAL THERMODYNAMICS, 1975, 7 (08) :787-794
[5]   PRESSURE-INDUCED DIASTEREOSELECTIVITY IN PHOTOCHEMICAL [2 + 2] CYCLOADDITION REACTIONS [J].
BUBACK, M ;
BUNGER, J ;
TIETZE, LF .
CHEMISCHE BERICHTE-RECUEIL, 1992, 125 (11) :2577-2582
[6]   EFFECTS OF HYDROSTATIC-PRESSURE ON THE LOCATION OF PRODAN IN LIPID BILAYERS AND CELLULAR MEMBRANES [J].
CHONG, PLG .
BIOCHEMISTRY, 1988, 27 (01) :399-404
[7]   RADICAL IONS AND PHOTOCHEMICAL CHARGE-TRANSFER PHENOMENA .22. PRESSURE-INDUCED DIASTEREOSELECTIVITY IN PHOTOINDUCED DIELS-ALDER REACTIONS [J].
CHUNG, WS ;
TURRO, NJ ;
MERTES, J ;
MATTAY, J .
JOURNAL OF ORGANIC CHEMISTRY, 1989, 54 (20) :4881-4887
[8]   PRESSURE EFFECTS ON BIMOLECULAR REDUCTIVE QUENCHING OF THE PLATINUM(II) DIMER PT2(MU-ETA-2-H2P2O5)4(4-) BY ORGANIC SUBSTRATES [J].
CRANE, DR ;
FORD, PC .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1990, 112 (19) :6871-6875
[9]   PRESSURE EFFECTS ON THE COMPETITIVE ENERGY AND ELECTRON-TRANSFER QUENCHING OF THE MLCT EXCITED-STATE OF CU(DPP)2+ (DPP = 2,9-DIPHENYL-1,10-PHENANTHROLINE) BY CRL3 (L = BETA-DIONATO LIGANDS) AND OTHER QUENCHERS IN SOLUTION [J].
CRANE, DR ;
FORD, PC .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1991, 113 (22) :8510-8516
[10]   ALKENE ISOMERIZATION - IMPROVED ONE-STEP SYNTHESIS OF TRANS CYCLOOCTENE [J].
DEYRUP, JA ;
BETKOUSK.M .
JOURNAL OF ORGANIC CHEMISTRY, 1972, 37 (22) :3561-&