(-)-copalol | 21738-29-4

• 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: (-)-copalol
• 英文别名: ent-labda-8(17),13E-dien-15-ol；(-)-ent-8(17),13(E)-Labdadien-15-ol；ent-copalol；(-)-Ent-copalol；(E)-5-[(1R,4aR,8aR)-5,5,8a-trimethyl-2-methylidene-3,4,4a,6,7,8-hexahydro-1H-naphthalen-1-yl]-3-methylpent-2-en-1-ol
• CAS: 21738-29-4
• 化学式: C₂₀H₃₄O
• 分子量: 290.489
• InChiKey: NERNKRPBSOBEHC-PGHZQYBFSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.1
• 重原子数：
  21
• 可旋转键数：
  4
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.8
• 拓扑面积：
  20.2
• 氢给体数：
  1
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  (-)-copalol 在 2,4,6-三甲基吡啶 、 甲基磺酰氯 、 lithium chloride 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 反应 1.5h， 生成 ent-copalyl chloride
  参考文献：
  名称：

  Functional characterization of the rice kaurene synthase-like gene family

  摘要：

  The rice (Oryza sativa) genome contains a family of kaurene synthase-like genes (OsKSL) presumably involved in diterpenoid biosynthesis. While a number of OsKSL enzymes have been functionally characterized, several have not been previously investigated, and the gene family has not been broadly analyzed. Here we report cloning of several OsKSL genes and functional characterization of the encoded enzymes. In particular, we have verified the expected production of ent-kaur-16-ene by the gibberellin phytohormone biosynthesis associated OsKS1 and demonstrated that OsKSL3 is a pseudo-gene, while OsKSL5 and OsKSL6 produce ent-(iso)kaur-15-ene. Similar to previous reports, we found that our sub-species variant of OsKSL7 produces ent-cassa-12,15-diene, OsKSL10 produces ent-(sandaraco)pimar-8(14),15-diene, and OsKSL8 largely syn-stemar-13-ene, although we also identified syn-stemod-12-ene as an alternative product formed in similar to 20% of the reactions catalyzed by OsKSL8. Along with our previous reports identifying OsKSL4 as a syn-pimara-7,15-diene synthase and OsKSL11 as a syn-stemod-13(17)-ene synthase, this essentially completes biochemical characterization of the OsKSL gene family, enabling broader analyses. For example, because several OsKSL enzymes are involved in phytoalexin biosynthesis and their gene transcription is inducible, promoter analysis was used to identify a pair of specifically conserved motifs that may be involved in transcriptional up-regulation during the rice plant defense response. Also examined is the continuing process of gene evolution in the OsKSL gene family, which is particularly interesting in the context of very recently reported data indicating that a japonica sub-species variant of OsKSL5 produces ent-pimara-8(14),15-diene, rather than the ent-(iso)kaur-15-ene produced by the indica sub-species variant analyzed here. (c) 2006 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.phytochem.2006.10.016
• 作为产物：
  描述：

  13-oxo-14,15-bis-nor-ent-labd-8(17)-ene 在 sodium hydride 、 二异丁基氢化铝 作用下， 以 四氢呋喃 、 乙醚 、 正己烷 为溶剂， 反应 26.0h， 生成 (-)-copalol
  参考文献：
  名称：

  通过光学分辨率的Drimane倍半萜烯和Labdane二萜烯的通用合成中间体的光学拆分，可完成Copalol的两种对映异构体的全合成

  摘要：

  Copalol（6）的两个对映异构体的总合成是通过消旋二醇[（±）-4 ]的旋光拆分完成的，该消旋二醇是drimane倍半萜和拉丹烷二萜的通用合成中间体。（±）-4和Boc-1-脯氨酸之间的酯化反应得到非对映体的单酯对（5a和5b），可以通过快速柱色谱法轻松分离。拆分的5a和5b进行PDC氧化，然后进行β消除，得到旋光的烯酮（9和ent -9）。两种烯酮分别以36％的收率和（-）-转化为（+）- 6在以下五个步骤中以26％的产率获得6：（1）Sakurai反应（TiCl 4促进烯丙基硅烷的共轭加成），（2）Wittig亚甲基化，（3）Wacker氧化，（4）Horner-Emmons反应和（5）DIBAL -H减少。

  DOI：

  10.1016/s0040-4020(00)00791-2

文献信息

• Substrate specificity of Rv3378c, an enzyme from Mycobacterium tuberculosis, and the inhibitory activity of the bicyclic diterpenoids against macrophagephagocytosis
  作者：Tsutomu Hoshino、Chiaki Nakano、Takahiro Ootsuka、Yosuke Shinohara、Takashi Hara

  DOI：10.1039/c0ob00884b

  日期：——

  The Rv3378c gene product from Mycobacterium tuberculosis encodes a diterpene synthase to produce tuberculosinol (3), 13R-isotuberculosinol (4a), and 13S-isotuberculosinol (4b) from tuberculosinyl diphosphate (2). The product distribution ratios are 1 : 1 for 3 to 4 and 1 : 3 for 4a to 4b. The substrate specificity of the Rv3378c-encoded enzyme was examined. The 3 labdadienyl diphosphates, copalyl diphosphate (CDP) (7), ent-CDP (8), and syn-CDP (9), underwent the conversion reaction, with good yields (67–78%). Copalol (23) and manool (24) were produced from 7, ent-copalol (25) and ent-manool (26) from 8, and syn-copalol (27) and vitexifolin A (28) from 9. The ratio of 23 to 24 was 40 : 27, that of 25:26 was 22 : 50, and that of 27:28 was 16 : 62. Analysis on a GC-MS chromatograph equipped with a chiral column revealed that 24, 26, and 28 consisted of a mixture of 13R- (a) and 13S-stereoisomers (b) in the following ratio: ca. 1 : 1 for 24a to 24b, ca. 1 : 5 for 26a to 26b, and ca. 1 : 19 for 28a to 28b. The structures of these products indicate that the reactions of the 3 CDPs proceeded in the same fashion as that of 2. This is the first report on the enzymatic synthesis of natural diterpenes manool, ent-manool, and vitexifolin A. Both Rv3377c and Rv3378c genes are found in virulent Mycobacterium species, but not in avirulent species. We found that 3 and 4 inhibited the phagocytosis of opsonized zymosan particles by human macrophage-like cells. Interestingly, the inhibitory activity was synergistically increased by the coexistence of 3 and 4b. Other labdane-related diterpenes, 13–16 and 23–28, had little or no inhibitory activity. This synergistic inhibition by 3 and 4 may provide further advantage to the impairment of phagocyte function, which might contribute to pathogenicity of M. tuberculosis.

  结核分枝杆菌的 Rv3378c 基因产品编码一种二萜合成酶，可从结核苷二磷酸（2）中产生结核苷醇（3）、13R-异结核苷醇（4a）和 13S- 异结核苷醇（4b）。产物分布比为 1 ：3 和 4 的产物分布比为 1 : 1，4a 和 4b 的产物分布比为 1 ：4a 和 4b 的产物分布比分别为 1 : 1 和 1 : 3。对 Rv3378c 编码酶的底物特异性进行了研究。3 种拉巴二烯基二磷酸酯，即二磷酸 copalyl (CDP)（7）、二磷酸 ent-CDP（8）和二磷酸 syn-CDP（9）发生了转化反应，且收率良好（67-78%）。由 7 生成了 Copalol (23) 和 manool (24)，由 8 生成了 ent-copalol (25) 和 ent-manool (26)，由 9 生成了 syn-copalol (27) 和 vitexifolin A (28)：50，27:28 的比例为 16:62。在配有手性色谱柱的气相色谱-质谱仪上进行的分析表明，24、26 和 28 由 13R 立体异构体 (a) 和 13S 立体异构体 (b) 的混合物组成，比例如下：24a 和 24b 约为 1 ：24a 至 24b 约为 1 : 1，26a 至 26b 约为 1 ：26a 至 26b 约为 1 : 5，28a 至 28b 约为 1 ：28a 至 28b 的比例约为 1 : 19。这些产物的结构表明，3 个 CDPs 的反应过程与 2 的反应过程相同。 这是首次报道天然二萜马诺醇、ent-马诺醇和荆芥苷 A 的酶法合成。我们发现，3 和 4 可抑制类人巨噬细胞对蛋白溶解酶颗粒的吞噬作用。有趣的是，3 和 4b 同时存在时，其抑制活性会协同增强。其他与拉巴旦相关的二萜（13-16 和 23-28）几乎没有抑制活性。3 和 4 的这种协同抑制作用可能会进一步损害吞噬细胞的功能，从而导致结核杆菌的致病性。
• The structure and stereochemistry of diterpenes from trachylobium verrucosum Oliv.—V
  作者：G. Hugel、A.C. Oehlschlager、G. Ourisson

  DOI：10.1016/s0040-4020(01)82184-0

  日期：1966.1

  The isolation from Trachylobium verrucosum of seven new bicarbocyclic diterpenes, possessing the (−) labdane skeleton, is described. Their structure have been determined as 4d, 6d, 6e, 6f, 7a, 8a and 10b. In addition, caryophyllene oxide (9), enantio labd-8(20), 13-diene-15 oic acid (4g), enantio labd-8(20)-en-15,18-dioic acid (6c), enantio labd-8(20)-en-15-oic acid (5b) and (−) 13-epimanool (10a)

  描述了七种新的具有（-）拉丹烷骨架的双碳环二萜与拟南芥的分离。已经确定它们的结构为4d，6d，6e，6f，7a，8a和10b。另外，石竹烯氧化物（9），对映LABD -8（20），13-二烯-15 OIC酸（4克），对映LABD -8（20） -烯-15,18-二酸（图6c），对映体labd -8（20）-en -15-油酸（5b）和（-）13-Epimanool（10a）已被分离。该树脂的成分与从该树的种子荚中提取的成分明显不同。后者主要包含与（-）贝壳杉烯有关的四碳环和五碳环的二萜。
• Diterpenes from Araucaria bidwilli
  作者：R Caputo

  DOI：10.1016/s0031-9422(00)91234-2

  日期：1974.2

  Abstract Eight diterpent acids of the labdane or clerodane type were obtained from the oleoresin of Araucaria bidwilli and characterized as their methyl esters.

  摘要 从南洋杉的油树脂中提取了八种劳丹型或氯罗丹型二萜酸，并表征为它们的甲酯。
• Neue labdan-derivate und andere inhaltsstoffe aus Relhania acerosa
  作者：Ferdinand Bohlmann、Jasmin Jakupovic

  DOI：10.1016/s0031-9422(00)84274-0

  日期：1979.1

  Abstract The investigation of Relhania acerosa afforded, in addition to known compounds, three new labdane derivatives, two of which are esterified with succinic acid and one which has an anomalous carbon skeleton. Furthermore, several new aromatic compounds are isolated, which are most probably degradated thymol derivatives. The structures are elucidated by spectroscopic methods and by some chemical

  摘要 除已知化合物外，对Relhania acerosa 的研究还提供了三种新的劳丹烷衍生物，其中两种用琥珀酸酯化，另一种具有异常碳骨架。此外，还分离了几种新的芳香族化合物，它们很可能是降解的百里酚衍生物。这些结构是通过光谱方法和一些化学转化来阐明的。一种新型拉丹的立体化学是通过部分合成建立的。简要讨论了化学分类情况。
• Dawson, Raymond M.; Godfrey, Ian M.; Hogg, Ronald W., Australian Journal of Chemistry, 1989, vol. 42, # 4, p. 561 - 580
  作者：Dawson, Raymond M.、Godfrey, Ian M.、Hogg, Ronald W.、Knox, John R.

  DOI：——

  日期：——