Structure of (+)-(7S,SS)-1,2,3,5,6,7-hexahydro-7-methyl-8-(p-tolylsulfinyl)-5-indoli zinone.
Structure of (+)-(7S,SS)-1,2,3,5,6,7-hexahydro-7-methyl-8-(p-tolylsulfinyl)-5-indoli zinone.
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( )-(7S,SS)-1,2,3,5,6,7-六氢-7-甲基-8-(对甲苯亚磺酰基)-5-吲哚嗪酮的结构。
DOI：
10.1107/s0108270189011601
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发表时间：
1990
期刊：
影响因子：
--
通讯作者：
Robinson,PD
中科院分区：
文献类型：
--
作者：
Hua,DH;Bharathi,SN;Tsujimoto,A;Robinson,PD
CI6HI9NO2S, Mr--289-39, orthorhombic, P2, 212,, a= 11.467 (5), b= 17.207 (8), c= 7.566 (4) A, V= 1493 (2) A3, Z= 4, Dx= 1-29 g cm-3, A (Mo Kte)= 0.71069/~,/z--2.07 cm-1, F (000)= 616, T= 296 K, R= 0.049, 928 unique observed reflections. The structure determination combined with the known S configuration at the sulfur site discloses the stereochemistry of the title compound to be 7S and SS. Introduction. In the studies involving the enantio-selective synthesis of biologically active indolizidines, the asymmetric addition reactions of the anion derived from (+)-(SR)-3, 4-dihydro-5-(p-tolylsulfinyl-methyl)-2H-pyrrole (I)(Morrison & Boyd, 1987) and trans-methyl or-ethyl crotonates were investigated. The reaction afforded 80% yield (isolated) of the title compound (II) and its 7R isomer (III)(ratio of 1: 2; same ratios were obtained in either methyl or ethyl crotonate reactions). The relative stereochemistry at the S atom and C (7) of (II) was proven by this X-ray study. This proof, in turn, provides firm evidence of the stereochemical course followed in asymmetric addition reactions of chiral a-sulfinyl ketimine anions [such as (I)] with trans-alkyl crotonates. Experimental. All new compounds displayed satis-factory'H NMR (400 MHz), t3C NMR (100 MHz), UV, IR and low-resolution mass spectra (both EI and CI) and satisfactory elemental analysis. Title compound,(+)-(7S, SS)-1, 2, 3, 5, 6, 7-hexahydro-7-methyl-8-(p-tolylsulfinyl)-5-indolizinone (II), and related compound,(-)-(7R, SS), l, 2, 3, 5, 6, 7-hexa-hydro-7-methyl-8-(p-tolylsulfinyl)-5-indolizinone (III) prepared as follows. To a cold (195 K) solution of 1 g (4.52 mmol) of (+)-SR-3, 4-dihydro-5-(p-tolyl-sulfmylmethyl)-2H-pyrrole (I)[ketimine (I) prepared by treating 3 equivalents 3, 4-dihydro-5-methyl-2H-
