[(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] (2R)-5-methyl-2-prop-1-en-2-ylhex-4-enoate | 170710-33-5

• 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: [(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] (2R)-5-methyl-2-prop-1-en-2-ylhex-4-enoate
• CAS: 170710-33-5
• 化学式: C₂₂H₃₄O₇
• 分子量: 410.508
• InChiKey: QETWSIAAWWBDMI-YYCWZVFASA-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：
  7
• 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：

  [(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] (2R)-5-methyl-2-prop-1-en-2-ylhex-4-enoate 在 lithium aluminium tetrahydride 作用下， 以 四氢呋喃 为溶剂， 反应 4.0h， 以98%的产率得到熏衣草醇
  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：

  5-Methyl-2-(1'-methylethyliden)-4-hexensaeure-ethylester 在 4-二甲氨基吡啶 、 氢氧化钾 、 4 A molecular sieve 、 N,N'-二环己基碳二亚胺 作用下， 以 乙醇 、 二氯甲烷 为溶剂， 反应 6.0h， 生成 [(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] (2R)-5-methyl-2-prop-1-en-2-ylhex-4-enoate
  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

• Asymmetric <i>α</i>-Alkylation of <i>α</i>,<i>β</i>-Unsaturated Esters. Application to the Synthesis of (R)-Lavandulol, (R)-Sesquilavandulol and Related Trifluoromethyl Compounds
  作者：S. Faure、O. Piva

  DOI：10.1055/s-1998-1960

  日期：1998.12

  Diastereoselective α-alkylation/deconjugation of esters of diacetone D-glucose has been performed and applied to the syntheses of (R)-lavandulol, (R)-sesquilavandulol with de up to 74%. The same reaction performed with trifluoromethyl derivatives was also achieved but without significant diastereoselectivity.

  二丙酮-D-葡萄糖酯的非对映选择性α-烷基化/脱共轭反应已经完成，并应用于(R)-薰衣草醇和(R)-倍半�薰衣草醇的合成，其对映体过量率（de值）高达74%。同样的反应在三氟甲基衍生物上也实现了，但没有显著的非对映选择性。
• 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.