(1S)-(-)-verbenone

• 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: (1S)-(-)-verbenone
• 英文别名: (1S,5S)-4,6,6-trimethylbicyclo[3.1.1]heptan-2-one
• 化学式: C₁₀H₁₆O
• 分子量: 152.236
• InChiKey: QKGNSWNKNMFYRE-ZHFSPANRSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.1
• 重原子数：
  11
• 可旋转键数：
  0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.9
• 拓扑面积：
  17.1
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  (1S)-(-)-verbenone 在 双氧水 、 sodium hydroxide 、 lithium aluminium tetrahydride 作用下， 生成 (1R,2R,6S)-3-methyl-6-(1-methylethenyl)cyclohex-3-ene-1,2-diol
  参考文献：
  名称：

  含有烷基取代芳族部分的 4,7-Dimethyl-3,4,4a,5,8,8a-Hexahydro-2-Chromen-4,8-​​Diols 的合成和镇痛活性

  摘要：

  通过对单萜对薄荷醇1,8-二烯-5,6-二醇与4-烷基取代的芳香醛反应，制备了一系列具有六氢-2H-色烯骨架的新型杂环化合物。与与苯甲醛的类似反应相比，向醛芳环中添加小的烷基取代基（甲基和乙基）可提高六氢色烯的产率。然而，添加支链取代基（异丙基）和更长的丁基和辛基部分会降低目标化合物的产率。随着烷基取代基的延长，反应的立体选择性发生变化。研究了所得产物的镇痛活性。

  DOI：

  10.1007/s10600-017-2202-1
• 作为产物：
  描述：

  马鞭草烯醇 在 F₄₂₀ 、 F⁴²⁰-dependent glucose-6-phosphate dehydrogenase 、 Mycobacterium smegmatis flavin/deazaflavin oxidoreductase A MSMEG_2850 作用下， 以 甲醇 为溶剂， 生成 (1S)-(-)-verbenone
  参考文献：
  名称：

  Asymmetric Ene-Reduction of α,β-Unsaturated Compounds by F₄₂₀-Dependent Oxidoreductases A Enzymes from Mycobacterium smegmatis

  摘要：

  烯还原酶可立体选择性地还原烯与电子萃取基团的共轭，这种方法已被广泛应用于精细化学品的商业制备。尽管已知有多个不同的酶家族具有烯还原酶活性，但对老黄酶（OYE）家族的研究最为深入。最近的研究表明，属于黄素/去氮黄素氧化还原酶（FDOR）超家族的烯还原酶子集表现出的对映选择性通常与 OYE 家族的对映选择性互补。这些酶属于使用不常见的脱氮黄素辅助因子 F420 的几个 FDOR 亚群之一。在这里，我们研究了 FDOR-A 亚群的几种酶，用 20 种不同的化合物鉴定了它们的底物范围和对映体选择性，确定了可以立体选择性还原多种化合物的酶（MSMEG_2027 和 MSMEG_2850）。例如，MSMEG_2027 能催化柠檬醛的两种异构体完全转化为(R)-香茅醛，ee 为 99%；MSMEG_2850 能催化酮异佛尔酮完全转化为(S)-来伏二酮，ee 为 99%。蛋白质晶体学与计算对接相结合，使观察到的两种酶的立体选择性得到了机理上的合理解释。这些发现进一步支持了 FDOR 和 OYE 系列烯还原酶显示出一般的立体互补性，并突出了它们在不对称烯还原中的潜在价值。

  DOI：

  10.1021/acs.biochem.2c00557

文献信息

• Guest/Host Relationships in the Synthesis of the Novel Cage-Based Zeolites SSZ-35, SSZ-36, and SSZ-39
  作者：Paul Wagner、Yumi Nakagawa、Greg S. Lee、Mark E. Davis、Saleh Elomari、Ronald C. Medrud、S. I. Zones

  DOI：10.1021/ja990722u

  日期：2000.1.1

  Here, we report the synthesis and structure of three high-silica molecular sieves, SSZ-35, SSZ-36, and SSZ-39, that are prepared from a library of 37 different cyclic and polycyclic quaternized amine molecules that are used as structure-directing agents (SDAs). The size and shape of the quaternized amine molecules are purposely designed in order to obtain novel zeolite structures, and the synthesis of these molecules is presented. The selectivity for the three molecular sieve phases is found to depend on both the SDA and the degree of heteroatom lattice substitution of Al3+ or B3+ in the silicate framework. Molecular modeling is utilized to probe the effects of the nonbonded SDA/zeolite-framework interaction energy on the selectivity for the observed molecular sieve phase. The Rietveld refinement of the powder X-ray data confirms the structure of the SSZ-39 zeolite to be isomorphous with the aluminophosphate molecular sieve, SAPO-LS (AEI). The structure of SSZ-36 is found to possess a range of fault probabilities between the two-dimensional channel system, end-member polymorphs, ITQ-3 and RUB-13 (International Zeolite Association Codes ITE and RTH, respectively). The SSZ-35 structure is reported to contain a one-dimensional pore system possessing stacked cages circumscribed by alternating rings of 10 and 18 tetrahedral atoms (10- and 18-membered rings).
• A selective reduction of α,β-unsaturated ketones
  作者：Maria Luiza A. von Holleben、Mônica Zucolotto、Claudia A. Zini、Eduardo R. Oliveira

  DOI：10.1016/s0040-4020(01)80811-5

  日期：1994.1

  A selective hydrogenation of carbon-carbon double bond of alpha,beta-unsaturated ketones are obtained when a mixture of limonene, alpha,beta-unsaturated ketone and 10% Pd/C is refluxed with vigorous stirring for 15-45 min. The best results are obtained when a molar ratio limonene:alpha,beta-unsaturated ketone of 3:1 and 4 molar % palladium/ketone are used. The stereoselectivity is similar to the results obtained when H-2 and Pd/C have been used in neutral solvent.
• Masui, Masaichiro; Hosomi, Katsuko; Tsuchida, Keiichi, Chemical and pharmaceutical bulletin, 1985, vol. 33, # 11, p. 4798 - 4802
  作者：Masui, Masaichiro、Hosomi, Katsuko、Tsuchida, Keiichi、Ozaki, Shigeko

  DOI：——

  日期：——
• Synthesis and Analgesic Activity of 4,7-Dimethyl-3,4,4a,5,8,8a-Hexahydro-2-Chromen-4,8-Diols Containing Alkyl-Substituted Aromatic Moieties
  作者：O. S. Patrusheva、A. V. Pavlova、D. V. Korchagina、T. G. Tolstikova、K. P. Volcho、N. F. Salakhutdinov

  DOI：10.1007/s10600-017-2202-1

  日期：2017.11

  para-mentha-1,8-diene-5,6-diol with 4-alkyl-substituted aromatic aldehydes. Adding small alkyl substituents (methyl and ethyl) to the aldehyde aromatic ring increased the yields of hexahydrochromenes as compared with the analogous reaction with benzaldehyde. However, adding a branched substituent (isopropyl) and longer butyl and octyl moieties reduced the yields of the target compounds. The stereoselectivity

  通过对单萜对薄荷醇1,8-二烯-5,6-二醇与4-烷基取代的芳香醛反应，制备了一系列具有六氢-2H-色烯骨架的新型杂环化合物。与与苯甲醛的类似反应相比，向醛芳环中添加小的烷基取代基（甲基和乙基）可提高六氢色烯的产率。然而，添加支链取代基（异丙基）和更长的丁基和辛基部分会降低目标化合物的产率。随着烷基取代基的延长，反应的立体选择性发生变化。研究了所得产物的镇痛活性。
• Asymmetric Ene-Reduction of α,β-Unsaturated Compounds by F₄₂₀-Dependent Oxidoreductases A Enzymes from <i>Mycobacterium smegmatis</i>
  作者：Suk Woo Kang、James Antoney、Rebecca L. Frkic、David W. Lupton、Robert Speight、Colin Scott、Colin J. Jackson

  DOI：10.1021/acs.biochem.2c00557

  日期：2023.2.7

  The stereoselective reduction of alkenes conjugated to electron-withdrawing groups by ene-reductases has been extensively applied to the commercial preparation of fine chemicals. Although several different enzyme families are known to possess ene–reductase activity, the old yellow enzyme (OYE) family has been the most thoroughly investigated. Recently, it was shown that a subset of ene-reductases belonging to the flavin/deazaflavin oxidoreductase (FDOR) superfamily exhibit enantioselectivity that is generally complementary to that seen in the OYE family. These enzymes belong to one of several FDOR subgroups that use the unusual deazaflavin cofactor F420. Here, we explore several enzymes of the FDOR-A subgroup, characterizing their substrate range and enantioselectivity with 20 different compounds, identifying enzymes (MSMEG_2027 and MSMEG_2850) that could reduce a wide range of compounds stereoselectively. For example, MSMEG_2027 catalyzed the complete conversion of both isomers of citral to (R)-citronellal with 99% ee, while MSMEG_2850 catalyzed complete conversion of ketoisophorone to (S)-levodione with 99% ee. Protein crystallography combined with computational docking has allowed the observed stereoselectivity to be mechanistically rationalized for two enzymes. These findings add further support for the FDOR and OYE families of ene-reductases displaying general stereocomplementarity to each other and highlight their potential value in asymmetric ene-reduction.

  烯还原酶可立体选择性地还原烯与电子萃取基团的共轭，这种方法已被广泛应用于精细化学品的商业制备。尽管已知有多个不同的酶家族具有烯还原酶活性，但对老黄酶（OYE）家族的研究最为深入。最近的研究表明，属于黄素/去氮黄素氧化还原酶（FDOR）超家族的烯还原酶子集表现出的对映选择性通常与 OYE 家族的对映选择性互补。这些酶属于使用不常见的脱氮黄素辅助因子 F420 的几个 FDOR 亚群之一。在这里，我们研究了 FDOR-A 亚群的几种酶，用 20 种不同的化合物鉴定了它们的底物范围和对映体选择性，确定了可以立体选择性还原多种化合物的酶（MSMEG_2027 和 MSMEG_2850）。例如，MSMEG_2027 能催化柠檬醛的两种异构体完全转化为(R)-香茅醛，ee 为 99%；MSMEG_2850 能催化酮异佛尔酮完全转化为(S)-来伏二酮，ee 为 99%。蛋白质晶体学与计算对接相结合，使观察到的两种酶的立体选择性得到了机理上的合理解释。这些发现进一步支持了 FDOR 和 OYE 系列烯还原酶显示出一般的立体互补性，并突出了它们在不对称烯还原中的潜在价值。