bis<(R)-1-phenylbutyl>malonate | 225923-04-6

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: bis<(R)-1-phenylbutyl>malonate
• 英文别名: bis[(1R)-1-phenylbutyl] propanedioate
• CAS: 225923-04-6
• 化学式: C₂₃H₂₈O₄
• 分子量: 368.473
• InChiKey: IIXLAWUIGIOABM-NHCUHLMSSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.7
• 重原子数：
  27
• 可旋转键数：
  12
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.39
• 拓扑面积：
  52.6
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  富勒烯 、 bis<(R)-1-phenylbutyl>malonate 在 碘 、 1,8-二氮杂双环[5.4.0]十一碳-7-烯 作用下， 以 甲苯 为溶剂， 以40%的产率得到bis<(R)-1-phenylbutyl> 1,2-methano<70>fullerene-71,71-dicarboxylate
  参考文献：
  名称：

  Achiral and Chiral Higher Adducts of C70 byBingel Cyclopropanation

  摘要：

  Five optically active isomeric C-70 bis-adducts with (R)-configured chiral malonate addends were prepared by Bingel cyclopropanation (Scheme 1) and their circular dichroism (CD) spectra investigated in comparison to those of the corresponding five bis-adducts with (S)-configured addends (Fig. 2). Pairs of diastereoisomers, in which the inherently chiral addition patterns on the fullerene surface have an enantiomeric relationship, display mirror-image shaped CD spectra that are nearly identical to those of the corresponding pairs of enantiomers (Fig. 3, b and c). This result demonstrates that the Cotton effects arising from the chiral malonate addends are negligible as compared to the chiroptical contribution of the chirally functionalized fullerene chromophore. A series of four stereoisomeric tetrakis-adducts (Fig. 4) was prepared by Bingel cyclopropanation starting from four stereoisomeric bis-adducts. A comparison of the CD spectra of both series of compounds showed that the magnitude of the Cotton effects does not decrease with increasing degree of functionalization (Fig. 5). Bingel cyclopropanations of C-70 in Me2SO are dramatically faster than in apolar solvents such as CCl4, and the reaction of bis-adducts (+/-)-13 and 15 with large excesses of diethyl 2-bromomalonate and DBU generate 1, via the intermediacy of defined tetrakis-adducts (+/-)-16 and 17, respectively, a series of higher adducts including hexakis-, heptakis-, and octakis-adducts (Table 1). A high regioselectivity was observed up to the stage of the hexakis-adducts, whereas this selectivity became much reduced at higher stages of addition. The regioselectivity of the nucleophilic cyclopropanations of C-70 correlates with the coefficients of the LUMO (lowest unoccupied molecular orbital) and LUMO + 1 at the positions of preferential attack calculated by restricted Hartree-Fock self-consistent field (RHF-SCF) methods (Figs. 9-11). Based on predictions from molecular-orbital calculations (Fig. II) and the analysis of experimental C-13-NMR data (Fig. 7,a), the structure of a unique hexakis-adduct ((+/-)-22, Fig. 12),prepared from (+/-)-13, was assigned. The C-2-symmetrical compound contains four 6-6-closed methanofullerene sub-structures in its polar regions (at the bonds C(1)-C(2), C(31)-C(32), C(54)-C(55),and C(59)-C(60)), and two 6-5-open methanofullerene sub-structures parallel to the equator (at C(22)- C(23) and C(26)- C(27)). The 6-5-open sub-structures are formed by malonate additions to near-equatorial 6-5 bonds with enhanced LUMO coefficients: followed by valence isomerization (Fig. 12).

  DOI：

  10.1002/(sici)1522-2675(19990210)82:2<261::aid-hlca261>3.0.co;2-x
• 作为产物：
  描述：

  (R)-(+)-1-苯基-1-丁醇 、 丙二酰氯 在 吡啶 作用下， 以 二氯甲烷 为溶剂， 以70%的产率得到bis<(R)-1-phenylbutyl>malonate
  参考文献：
  名称：

  Achiral and Chiral Higher Adducts of C70 byBingel Cyclopropanation

  摘要：

  Five optically active isomeric C-70 bis-adducts with (R)-configured chiral malonate addends were prepared by Bingel cyclopropanation (Scheme 1) and their circular dichroism (CD) spectra investigated in comparison to those of the corresponding five bis-adducts with (S)-configured addends (Fig. 2). Pairs of diastereoisomers, in which the inherently chiral addition patterns on the fullerene surface have an enantiomeric relationship, display mirror-image shaped CD spectra that are nearly identical to those of the corresponding pairs of enantiomers (Fig. 3, b and c). This result demonstrates that the Cotton effects arising from the chiral malonate addends are negligible as compared to the chiroptical contribution of the chirally functionalized fullerene chromophore. A series of four stereoisomeric tetrakis-adducts (Fig. 4) was prepared by Bingel cyclopropanation starting from four stereoisomeric bis-adducts. A comparison of the CD spectra of both series of compounds showed that the magnitude of the Cotton effects does not decrease with increasing degree of functionalization (Fig. 5). Bingel cyclopropanations of C-70 in Me2SO are dramatically faster than in apolar solvents such as CCl4, and the reaction of bis-adducts (+/-)-13 and 15 with large excesses of diethyl 2-bromomalonate and DBU generate 1, via the intermediacy of defined tetrakis-adducts (+/-)-16 and 17, respectively, a series of higher adducts including hexakis-, heptakis-, and octakis-adducts (Table 1). A high regioselectivity was observed up to the stage of the hexakis-adducts, whereas this selectivity became much reduced at higher stages of addition. The regioselectivity of the nucleophilic cyclopropanations of C-70 correlates with the coefficients of the LUMO (lowest unoccupied molecular orbital) and LUMO + 1 at the positions of preferential attack calculated by restricted Hartree-Fock self-consistent field (RHF-SCF) methods (Figs. 9-11). Based on predictions from molecular-orbital calculations (Fig. II) and the analysis of experimental C-13-NMR data (Fig. 7,a), the structure of a unique hexakis-adduct ((+/-)-22, Fig. 12),prepared from (+/-)-13, was assigned. The C-2-symmetrical compound contains four 6-6-closed methanofullerene sub-structures in its polar regions (at the bonds C(1)-C(2), C(31)-C(32), C(54)-C(55),and C(59)-C(60)), and two 6-5-open methanofullerene sub-structures parallel to the equator (at C(22)- C(23) and C(26)- C(27)). The 6-5-open sub-structures are formed by malonate additions to near-equatorial 6-5 bonds with enhanced LUMO coefficients: followed by valence isomerization (Fig. 12).

  DOI：

  10.1002/(sici)1522-2675(19990210)82:2<261::aid-hlca261>3.0.co;2-x