cis-verbanone | 473-66-5

• 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: cis-verbanone
• 英文别名: verbanone；(1R,4S,5R)-4,6,6-trimethylbicyclo[3.1.1]heptan-2-one
• CAS: 473-66-5
• 化学式: C₁₀H₁₆O
• 分子量: 152.236
• InChiKey: QKGNSWNKNMFYRE-RNJXMRFFSA-N

物化性质

• 沸点：
  84 °C(Press: 8 Torr)
• 密度：
  0.9644 g/cm3

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：

  cis-verbanone 在 lithium aluminium tetrahydride 作用下， 生成 neoisoverbanol
  参考文献：
  名称：

  用烟草培养细胞对单环和双环单萜类化合物进行生物转化的对映选择性

  摘要：

  研究了对薄荷烷和双环 [2.2.1] 和 [3.1.1] 庚烷衍生物的对映体对与烟草培养细胞的生物转化。发现(i)培养的细胞区分对-薄荷醇-2-醇和双环[2.2.1]庚烷-2-醇和双环[3.1.1]庚烷-3-醇衍生物的对映异构体，并对映选择性转化将这些醇转化为相应的酮，(ii) 细胞高度还原 p-menthan-2-one 衍生物的羰基，但不还原 p-menthan-3-ones 的羰基，以及 (iii) 细胞区分双环[3.1.1]hept-2-en-4-one（verbenone）的对映异构体，并对映选择性还原（1S，5S）-对映异构体的C-C双键。

  DOI：

  10.1246/bcsj.61.869
• 作为产物：
  描述：

  2-蒎烯聚合物 在 sodium tetrahydroborate 、 nickel(II) chloride hexahydrate 、 lead(IV) tetraacetate 作用下， 以 甲醇 为溶剂， 生成 cis-verbanone
  参考文献：
  名称：

  Synthesis of new enantiomerically pure β-amino alcohols of the pinane series

  摘要：

  A series of new beta-amino alcohols with pinane structure, (+)- and (aEuro')-3 alpha-amino-10 beta-pinan-4 beta-ols, 4 beta-amino-10 beta-pinan-3 alpha-ol, and 4 alpha-amino-10 beta-pinan-3 alpha-ol have been synthesized with the goal of using them as organocatalysts in the aldol reaction of isatin with acetone.

  DOI：

  10.1134/s1070428017030046

文献信息

• Copper + Nickel-in-Charcoal (Cu−Ni/C): A Bimetallic, Heterogeneous Catalyst for Cross-Couplings
  作者：Bruce H. Lipshutz、Danielle M. Nihan、Ekaterina Vinogradova、Benjamin R. Taft、Žarko V. Bošković

  DOI：10.1021/ol801676u

  日期：2008.10.2

  catalyst composed of copper and nickel oxide particles supported within charcoal has been developed. It catalyzes cross-couplings that traditionally use palladium, nickel, or copper, including Suzuki-Miyaura reactions, Buchwald-Hartwig aminations, vinylalane alkylations, etherifications of aryl halides, aryl halide reductions, asymmetric conjugate reductions of activated olefins, and azide-alkyne "click"

  已经开发出一种由负载在木炭中的铜和氧化镍颗粒组成的新型多相催化剂。它催化传统上使用钯、镍或铜的交叉偶联反应，包括 Suzuki-Miyaura 反应、Buchwald-Hartwig 胺化、乙烯基丙烷烷基化、芳基卤化物的醚化、芳基卤化物还原、活化烯烃的不对称共轭还原和叠氮炔”点击”反应。
• Enantioselectivity in the Biotransformation of Bicyclo[3.1.1]heptanes with the Cultured Cells of<i>Nicotiana tabacum</i>
  作者：Takayuki Suga、Hiroki Hamada、Toshifumi Hirata

  DOI：10.1246/cl.1987.471

  日期：1987.3.5

  The biotransformation of the enantiomeric pairs of bicyclo[3.1.1]heptane derivatives with the cultured cells of Nicotiana tabacum was investigated. The hydrogenation of the C–C double bond of verbenone took place enantioselectively in preference of the (1S,5S)-enantiomer and the hydrogen attack occurred stereospecifically from the re-face at its C-2. The oxidation of the hydroxyl group of neoisopinocampheol

  研究了双环[3.1.1]庚烷衍生物对映体对与烟草培养细胞的生物转化。马鞭草的 C-C 双键的氢化优先于 (1S,5S)-对映异构体发生对映选择性，氢攻击从其 C-2 的背面立体特异性地发生。新异松香酚羟基的氧化优先发生在 (1S,2S,3R,5R)-对映异构体中，而这种对映选择性氧化不是新异松醇的情况。
• Oxidation of secondary terpene alcohols by chlorine dioxide
  作者：L. L. Frolova、A. V. Popov、S. A. Rubtsova、A. V. Kuchin

  DOI：10.1007/s10600-009-9190-8

  日期：2008.11

  Secondary terpene alcohols cis- and trans-verbenol, neo-iso-verbanol, borneol, iso-borneol, and menthol were oxidized by chlorine dioxide into the corresponding ketones. It was shown that the nature of the solvent and catalyst and the structure of the starting compound, including the stereochemistry of the hydroxyl, influenced the oxidation process.

  次级萜醇顺-和反-香芹酮、neo-异香芹醇、冰片、异冰片和薄荷醇通过二氧化氯氧化成相应的酮。研究表明，溶剂和催化剂的性质以及起始化合物的结构，包括羟基的立体化学，都会影响氧化过程。
• Reactions of terpene alcohols and diols with chlorine dioxide in dimethylformamide
  作者：L. L. Frolova、A. V. Popov、L. V. Bezuglaya、I. N. Alekseev、P. A. Slepukhin、A. V. Kutchin

  DOI：10.1134/s107036321603018x

  日期：2016.3

  The system chlorine dioxide–dimethylformamide in combination with or without a catalytic amount of MoCl5, CeCl3, ZrOCl2, or VO(acac)2 induces oxidative chlorination of a number of bicyclic terpene alcohols and vicinal diols. 2α-Chloropinan-3-one, 3α-chloro-10β-pinan-4-one, 5α-chloro-3α-hydroxycaran-4-one, 5β-chloro-3β-hydroxycaran-4-one, and 4α-chloro-2α-hydroxypinan-3-one were thus synthesized in

  二氧化氯-二甲基甲酰胺体系与有或没有催化量的MoCl 5，CeCl 3，ZrOCl 2或VO（acac）2组合使用，会引起许多双环萜烯醇和邻二醇的氧化氯化反应。2α-氯丁酮3-one，3α-氯10β-pinan-4-one，5α-氯3α-hydroxycaran-4-one，5β-氯-3β-hydroxycaran-4-one和4α-chloro-2α因此以良好的制备产率合成了-羟基pinan-3-one。
• Several Monoterpenoid Bromination Products
  作者：L. L. Frolova、L. V. Bezuglaya、I. N. Alekseev、P. A. Slepukhin、A. V. Kuchin

  DOI：10.1007/s10600-014-0984-y

  日期：2014.7

  2α-Bromo,10β-pinanone-3 and 3α-bromo,10β-pinanone-4 were formed with 92–98% selectivity by bromination of isopinocamphone and cis-verbanone with Meldrum’s acid dibromide. 3α-Bromo, 10β-pinanone-4 was prepared for the first time. Its structure was confirmed by an XSA. Bromination of menthone by Meldrum’s acid dibromide formed mainly a mixture of diastereomeric 2-bromomenthones in a 2:1 ratio. Oxidative bromination of isopinocampheol by Ce(III)–LiBr–H2O2 caused rearrangement of the pinane structure into bornane and formed a mixture of 6-endo- and 6-exo-bromocamphor in a 5:1 ratio.

  2α-溴,10β-松油酮-3和3α-溴,10β-松油酮-4通过用Meldrum酸二溴化物对异松油酮和顺式-桉叶油酮进行溴化形成，选择性为92–98％。3α-溴,10β-松油酮-4是首次制备的。其结构通过XSA得到确认。Meldrum酸二溴化物对薄荷酮进行溴化主要形成比例为2:1的二种对映体2-溴薄荷酮的混合物。Ce(III)-LiBr-H2O2对异松油醇进行氧化溴化导致松油环结构重组为冰片烷，并形成比例为5:1的6-内-和6-外-溴樟脑的混合物。