(1,2:5,6-Di-O-isopropylidene-α-D-glucofuranos-3-O-yl)-2-(1'-methylethylidene)-5-methyl-4-hexenoate | 170710-37-9

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 异戊烯醇脂质
• 英文名称: (1,2:5,6-Di-O-isopropylidene-α-D-glucofuranos-3-O-yl)-2-(1'-methylethylidene)-5-methyl-4-hexenoate
• 英文别名: [(3aR,5R,6S,6aR)-5-[(4R)-2,2-dimethyl-1,3-dioxolan-4-yl]-2,2-dimethyl-3a,5,6,6a-tetrahydrofuro[2,3-d][1,3]dioxol-6-yl] 5-methyl-2-propan-2-ylidenehex-4-enoate
• CAS: 170710-37-9
• 化学式: C₂₂H₃₄O₇
• 分子量: 410.508
• InChiKey: YHXHMOYLUIXHQR-BFMVXSJESA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.9
• 重原子数：
  29
• 可旋转键数：
  6
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.77
• 拓扑面积：
  72.4
• 氢给体数：
  0
• 氢受体数：
  7

反应信息

• 作为反应物：
  描述：

  (1,2:5,6-Di-O-isopropylidene-α-D-glucofuranos-3-O-yl)-2-(1'-methylethylidene)-5-methyl-4-hexenoate 在 lithium aluminium tetrahydride 、 N,N-二甲基乙醇胺 作用下， 以 四氢呋喃 、 正戊烷 为溶剂， 反应 10.0h， 生成 熏衣草醇
  参考文献：
  名称：

  Enantio- and Diastereoselective Protonation of Photodienols: Total Synthesis of (R)-(-)-Lavandulol

  摘要：

  The total synthesis of (R)-(-)-lavandulol 1 has been achieved by asymmetric protonation of photodienols obtained from the irradiation of prochiral alpha,beta-unsaturated esters. The photodeconjugation of ethyl 5-methyl-2-(1'-methylethylidene)-4-hexenoate (3a), carried out in the presence of catalytic amounts of a beta-amino alcohol prepared from (+)-camphor, gives the beta,gamma-unsaturated isomer 2a in good yields but with moderate enantioselectivities (40% ee). In contrast, irradiation of the corresponding ester 3b, bearing the 1,2:5,6-di-O-isopropylidene-D-glucose group as a chiral alkoxy moiety, affords the deconjugated product 2b in high de (>95%). Simple reduction of the ester function with LiAlH4 gives (R)-(-)-lavandulol (1) without loss of optical purity.

  DOI：

  10.1021/jo00129a030
• 作为产物：
  描述：

  (1,2:5,6-Di-O-isopropylidene-α-D-glucofuranos-3-O-yl)-2-acetyl-5-methyl-4-hexenoate 在 copper(l) iodide 、 sodium hydride 作用下， 以 乙醚 为溶剂， 反应 3.0h， 生成 (1,2:5,6-Di-O-isopropylidene-α-D-glucofuranos-3-O-yl)-2-(1'-methylethylidene)-5-methyl-4-hexenoate
  参考文献：
  名称：

  Enantio- and Diastereoselective Protonation of Photodienols: Total Synthesis of (R)-(-)-Lavandulol

  摘要：

  The total synthesis of (R)-(-)-lavandulol 1 has been achieved by asymmetric protonation of photodienols obtained from the irradiation of prochiral alpha,beta-unsaturated esters. The photodeconjugation of ethyl 5-methyl-2-(1'-methylethylidene)-4-hexenoate (3a), carried out in the presence of catalytic amounts of a beta-amino alcohol prepared from (+)-camphor, gives the beta,gamma-unsaturated isomer 2a in good yields but with moderate enantioselectivities (40% ee). In contrast, irradiation of the corresponding ester 3b, bearing the 1,2:5,6-di-O-isopropylidene-D-glucose group as a chiral alkoxy moiety, affords the deconjugated product 2b in high de (>95%). Simple reduction of the ester function with LiAlH4 gives (R)-(-)-lavandulol (1) without loss of optical purity.

  DOI：

  10.1021/jo00129a030

文献信息

• Enantio- and Diastereoselective Protonation of Photodienols: Total Synthesis of (R)-(-)-Lavandulol
  作者：Olivier Piva

  DOI：10.1021/jo00129a030

  日期：1995.12

  The total synthesis of (R)-(-)-lavandulol 1 has been achieved by asymmetric protonation of photodienols obtained from the irradiation of prochiral alpha,beta-unsaturated esters. The photodeconjugation of ethyl 5-methyl-2-(1'-methylethylidene)-4-hexenoate (3a), carried out in the presence of catalytic amounts of a beta-amino alcohol prepared from (+)-camphor, gives the beta,gamma-unsaturated isomer 2a in good yields but with moderate enantioselectivities (40% ee). In contrast, irradiation of the corresponding ester 3b, bearing the 1,2:5,6-di-O-isopropylidene-D-glucose group as a chiral alkoxy moiety, affords the deconjugated product 2b in high de (>95%). Simple reduction of the ester function with LiAlH4 gives (R)-(-)-lavandulol (1) without loss of optical purity.