DETERMINATION OF THE ABSOLUTE-CONFIGURATION OF (+)-NEOPENTYL-1-D ALCOHOL BY NEUTRON AND X-RAY-DIFFRACTION ANALYSIS

被引:16
作者
YUAN, HSH
STEVENS, RC
BAU, R
MOSHER, HS
KOETZLE, TF
机构
[1] UNIV SO CALIF,DEPT CHEM,LOS ANGELES,CA 90089
[2] STANFORD UNIV,DEPT CHEM,STANFORD,CA 94305
[3] BROOKHAVEN NATL LAB,DEPT CHEM,UPTON,NY 11973
关键词
CHIRAL METHYLENE GROUP; DEUTERATED NEOPENTANOL; ALCOHOL DEHYDROGENASE;
D O I
10.1073/pnas.91.26.12872
中图分类号
O [数理科学和化学]; P [天文学、地球科学]; Q [生物科学]; N [自然科学总论];
学科分类号
07 ; 0710 ; 09 ;
摘要
The absolute configuration of (+)-neopentyl-1-d alcohol, prepared by the reduction of 2,2-dimethylpropanal-1-d by actively fermenting yeast, has been determined to be S by neutron diffraction. The neutron study was carried out on the phthalate half ester of neopentyl-1-d alcohol, crystallized as its strychnine salt. The absolute configuration of the (-)-strychninium cation was first determined by an x-ray anomalous dispersion study of its iodide salt. The chiral skeleton of strychnine then served as a reference from which the absolute configuration of the -O-CHD-C(CH3)(3) group of neopentyl phthalate was determined. Difference Fourier maps calculated from the neutron data showed unambiguously that the -O-CHD-C(CH3)(3) groups of both independent molecules in the unit cell had the S configuration. This work proves conclusively that the yeast system reduces aldehydes by delivering hydrogen to the re face of the carbonyl group. Crystallographic details: (-)-strychninium (+)-neopentyl-1-d phthalate, space group P2(1) (monoclinic), a = 18.564(6) Angstrom, b = 7.713(2) Angstrom, c = 23.361(8) Angstrom, beta = 94.18(4)degrees, V = 3336.0(5) Angstrom(3), Z = 2 (T = 100 K). Final agreement factors are R(F) = 0.073 for 2768 reflections collected at room temperature (x-ray analysis) and R(F) = 0.144 for 960 reflections collected at 100 R (neutron analysis).
引用
收藏
页码:12872 / 12876
页数:5
相关论文
共 49 条
[1]   ASYMMETRIC REDUCTIONS .13. OPTICALLY ACTIVE BENZYL-ALPHA-D ALCOHOL AND N-BUTYL-1-D ALCOHOL VIA REDUCTION BY ACTIVELY FERMENTING YEAST [J].
ALTHOUSE, VE ;
FEIGL, DM ;
SANDERSON, WA ;
MOSHER, HS .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1966, 88 (15) :3595-+
[2]   ASYMMETRIC REDUCTIONS .9. THE REDUCTION OF TRIMETHYLACETALDEHYDE-1-D BY ACTIVELY FERMENTING YEAST [J].
ALTHOUSE, VE ;
UEDA, K ;
MOSHER, HS .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1960, 82 (22) :5938-5941
[3]   DISPLACEMENT-REACTIONS OF NEOPENTYL-1-D TOSYLATE WITHOUT REARRANGEMENT AND OPTICAL-ROTATORY DISPERSION SPECTRA OF CHIRAL COMPOUNDS WITH 4 DIFFERENT GROUPS OF EITHER C3NU OR CALPHANU SYMMETRY ATTACHED TO A CENTRAL CARBON [J].
ANDERSON, PH ;
STEPHENS.B ;
MOSHER, HS .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1974, 96 (10) :3171-3177
[4]  
Arigoni D, 1969, TOP STEREOCHEM, V4, P127, DOI DOI 10.1002/9780470147139.CH4
[5]   STEREOSPECIFICITY OF SOME ENZYMIC REACTIONS [J].
BATTERSBY, AR ;
STAUNTON, J .
TETRAHEDRON, 1974, 30 (13) :1707-1715
[6]  
BEURSKENS PT, 1980, DIRDIF DIRECT METHOD
[7]   THE FOURIER SYNTHESIS OF THE CRYSTAL STRUCTURE OF STRYCHNINE SULPHATE PENTAHYDRATE [J].
BOKHOVEN, C ;
SCHOONE, JC ;
BIJVOET, JM .
ACTA CRYSTALLOGRAPHICA, 1951, 4 (03) :275-280
[8]   STRUCTURAL STUDIES ON POLYNUCLEAR OSMIUM CARBONYL HYDRIDES .7. CRYSTAL-STRUCTURE AND MOLECULAR-GEOMETRY OF (MU-H)2OS3RE2(CO)20 [J].
CHURCHILL, MR ;
HOLLANDER, FJ .
INORGANIC CHEMISTRY, 1978, 17 (12) :3546-3552
[9]   CALCULATION OF ABSORPTION CORRECTIONS FOR CAMERA AND DIFFRACTOMETER DATA [J].
COPPENS, P ;
LEISEROWITZ, L ;
RABINOVICH, D .
ACTA CRYSTALLOGRAPHICA, 1965, 18 :1035-+
[10]   ENZYMES AND STEREOCHEMISTRY [J].
CORNFORTH, JW .
TETRAHEDRON, 1974, 30 (12) :1515-1524