5,9-十一碳二烯酸,6,10-二甲基-,1,1-二甲基乙基酯,(E)- | 131938-67-5

• 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
• 中文名称: 5,9-十一碳二烯酸,6,10-二甲基-,1,1-二甲基乙基酯,(E)-
• 英文名称: tert-Butyl (5E)-6,10-Dimethylundeca-5,9-dienoate
• CAS: 131938-67-5
• 化学式: C₁₇H₃₀O₂
• 分子量: 266.424
• InChiKey: LWILDOGBEWNRSR-RVDMUPIBSA-N

物化性质

• 沸点：
  335.9±31.0 °C(Predicted)
• 密度：
  0.889±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  5.2
• 重原子数：
  19
• 可旋转键数：
  9
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.71
• 拓扑面积：
  26.3
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  5,9-十一碳二烯酸,6,10-二甲基-,1,1-二甲基乙基酯,(E)- 在 正丁基锂 、 草酰氯 、 二异丁基氢化铝 、 二甲基亚砜 、 1,8-二氮杂双环[5.4.0]十一碳-7-烯 、 三乙胺 、 二异丙胺 作用下， 以 二氯甲烷 、 甲苯 为溶剂， 反应 24.08h， 生成 <2E,2(E),7(E)>-2,7-Bis(4,8-dimethyl-3,7-nonadienyl)-2-octenedial
  参考文献：
  名称：

  Daphniphyllum alkaloids. 12. A proposed biosynthesis of the pentacylic skeleton. proto-Daphniphylline

  摘要：

  A biosynthetic proposal for the pentacyclic skeleton of the Daphniphyllum alkaloids is put forth (Scheme I) and various ramifications are examined experimentally. proto-Daphniphylline (11), the putative product of this hypothetical biogenesis, has been prepared by a convergent synthesis that starts with amide 14, alpha,beta-unsaturated ester 15, and homogeranyl iodide (Scheme II) and employs a highly efficient tetracyclization process previously used for the synthesis of (+/-)-methyl homosecodaphniphyllate (30) (Scheme III). The structure of proto-daphniphylline was confirmed by converting it into 30. The mechanism of the first stage of the tetracyclization process was investigated with the bis-homoneryl analogues 36/37. Treatment of these aldehydes successively with ammonia and acetic acid provided tetracyclic imine 38, suggesting that the cyclization reaction is a concerted Diels-Alder reaction rather than a stepwise process. Dialdehydes 27/28 were converted into 1,2-dihydro-proto-daphniphylline (29) by a version of the tetracyclization process wherein methylamine (or glycine) is substituted for ammonia. proto-Daphniphylline has also been prepared in a one-pot, two-stage process from the acyclic dialdehydes 51 and 55. Several versions of this pentacyclization process have been worked out. In the simplest, 51 or 55 is treated successively with ammonia and hot acetic acid to afford 11 in 15 +/- 2% yield. A slightly more elaborate protocol, a three-stage process that utilizes NaOH in benzene, ammonia in DMSO, and hot acetic acid, provided 11 in 49.4% overall yield. However, the most efficient pentacyclization process discovered employs successive reactions with methylamine (or glycine) and hot acetic acid. Under these conditions, 17,18-dihydro-proto-daphniphylline (29) is produced in 65% yield. The latter process is one of the most efficient reaction cascades ever discovered; it results in the formation of five rings, four carbon-carbon bonds, two carbon-nitrogen bonds, and concludes with the selective saturation of one of the three double bonds in proto-daphniphylline!

  DOI：

  10.1021/jo00035a009
• 作为产物：
  描述：

  (E)-9-iodo-2,6-dimethylnona-2,6-diene 、 乙酸叔丁酯锂烯醇化物 在 六甲基磷酰三胺 作用下， 以 四氢呋喃 为溶剂， 以77%的产率得到5,9-十一碳二烯酸,6,10-二甲基-,1,1-二甲基乙基酯,(E)-
  参考文献：
  名称：

  角鲨烯二磷酸的氮丙啶类似物对角鲨烯合酶的对映选择性抑制

  摘要：

  角鲨烯合酶通过环丙基羰基中间体、角鲨烯二磷酸 (PSPP)催化两分子 ( E , E )-法呢基二磷酸转化为角鲨烯。由于这种新反应构成了甾醇生物合成的第一个关键步骤，因此对该过程的立体化学和机制以及酶的选择性抑制剂的设计产生了相当大的兴趣和研究。本文报告了 PSPP 的五种外消旋和两种对映纯氮丙啶类似物的合成和表征，并评估了它们作为重组酵母角鲨烯合酶抑制剂的效力。关键的氮丙啶-2-甲醇中间体（6 - OH、7- OH和8 -OH）通过以下方式获得N-烷基化或通过(±)-、(2 R ,3 S )- 和 (2 S ,3 R )-2,3-氮丙啶法尼醇( 9 - OH)的N-酰化-还原序列保护为叔-丁基二甲基甲硅烷基醚。相应的甲磺酸盐与焦磷酸根和甲二膦酸根阴离子的S N 2 置换得到带有N-十一烷基、N-双香叶基和N- (α-亚甲基)双香叶基取代基的氮丙啶 2-二磷酸甲酯和甲二膦酸，作为 2,6,10-

  DOI：

  10.1021/jo100718z

文献信息

• Synthesis and Evaluation of Aziridine Analogues of Presqualene Diphosphate as Squalene Synthase Inhibitors
  作者：Ali Koohang、Robert M. Coates、David Owen、C. Dale Poulter

  DOI：10.1021/jo981833z

  日期：1999.1.1
• KAKEHI, AKIKAZU;ITO, SUKETAKA;SAKURAI, TOSIO;URUSHIDO, KUNIO;ISAWA, HIDET+, CHEM. AND PHARM. BULL., 38,(1990) N0, C. 2667-2675
  作者：KAKEHI, AKIKAZU、ITO, SUKETAKA、SAKURAI, TOSIO、URUSHIDO, KUNIO、ISAWA, HIDET+

  DOI：——

  日期：——
• PIETTRE, SERGE;HEATHCOCK, CLAYTON H., SCIENCE, 248,(1990) N962, C. 1532-1534
  作者：PIETTRE, SERGE、HEATHCOCK, CLAYTON H.

  DOI：——

  日期：——
• Enantioselective Inhibition of Squalene Synthase by Aziridine Analogues of Presqualene Diphosphate
  作者：Ali Koohang、Jessica L. Bailey、Robert M. Coates、Hans K. Erickson、David Owen、C. Dale Poulter

  DOI：10.1021/jo100718z

  日期：2010.7.16

  and N-(α-methylene)bishomogeranyl substituents as mimics for the 2,6,10-trimethylundeca-2,5,9-trienyl side chain of PSPP. The 2R,3S diphosphate enantiomer bearing the N-bishomogeranyl substituent corresponding in absolute stereochemistry to PSPP proved to be the most potent inhibitor (IC50 1.17 ± 0.08 μM in the presence of inorganic pyrophosphate), a value 4-fold less than that of its 2S,3R stereoisomer

  角鲨烯合酶通过环丙基羰基中间体、角鲨烯二磷酸 (PSPP)催化两分子 ( E , E )-法呢基二磷酸转化为角鲨烯。由于这种新反应构成了甾醇生物合成的第一个关键步骤，因此对该过程的立体化学和机制以及酶的选择性抑制剂的设计产生了相当大的兴趣和研究。本文报告了 PSPP 的五种外消旋和两种对映纯氮丙啶类似物的合成和表征，并评估了它们作为重组酵母角鲨烯合酶抑制剂的效力。关键的氮丙啶-2-甲醇中间体（6 - OH、7- OH和8 -OH）通过以下方式获得N-烷基化或通过(±)-、(2 R ,3 S )- 和 (2 S ,3 R )-2,3-氮丙啶法尼醇( 9 - OH)的N-酰化-还原序列保护为叔-丁基二甲基甲硅烷基醚。相应的甲磺酸盐与焦磷酸根和甲二膦酸根阴离子的S N 2 置换得到带有N-十一烷基、N-双香叶基和N- (α-亚甲基)双香叶基取代基的氮丙啶 2-二磷酸甲酯和甲二膦酸，作为 2,6,10-
• Daphniphyllum alkaloids. 12. A proposed biosynthesis of the pentacylic skeleton. proto-Daphniphylline
  作者：Clayton H. Heathcock、Serge Piettre、Roger B. Ruggeri、John A. Ragan、John C. Kath

  DOI：10.1021/jo00035a009

  日期：1992.4

  A biosynthetic proposal for the pentacyclic skeleton of the Daphniphyllum alkaloids is put forth (Scheme I) and various ramifications are examined experimentally. proto-Daphniphylline (11), the putative product of this hypothetical biogenesis, has been prepared by a convergent synthesis that starts with amide 14, alpha,beta-unsaturated ester 15, and homogeranyl iodide (Scheme II) and employs a highly efficient tetracyclization process previously used for the synthesis of (+/-)-methyl homosecodaphniphyllate (30) (Scheme III). The structure of proto-daphniphylline was confirmed by converting it into 30. The mechanism of the first stage of the tetracyclization process was investigated with the bis-homoneryl analogues 36/37. Treatment of these aldehydes successively with ammonia and acetic acid provided tetracyclic imine 38, suggesting that the cyclization reaction is a concerted Diels-Alder reaction rather than a stepwise process. Dialdehydes 27/28 were converted into 1,2-dihydro-proto-daphniphylline (29) by a version of the tetracyclization process wherein methylamine (or glycine) is substituted for ammonia. proto-Daphniphylline has also been prepared in a one-pot, two-stage process from the acyclic dialdehydes 51 and 55. Several versions of this pentacyclization process have been worked out. In the simplest, 51 or 55 is treated successively with ammonia and hot acetic acid to afford 11 in 15 +/- 2% yield. A slightly more elaborate protocol, a three-stage process that utilizes NaOH in benzene, ammonia in DMSO, and hot acetic acid, provided 11 in 49.4% overall yield. However, the most efficient pentacyclization process discovered employs successive reactions with methylamine (or glycine) and hot acetic acid. Under these conditions, 17,18-dihydro-proto-daphniphylline (29) is produced in 65% yield. The latter process is one of the most efficient reaction cascades ever discovered; it results in the formation of five rings, four carbon-carbon bonds, two carbon-nitrogen bonds, and concludes with the selective saturation of one of the three double bonds in proto-daphniphylline!