(1R,5S)-6,6-Dimethyl-bicyclo[3.1.1]heptan-2-one oxime | 90582-67-5

• 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
• 英文名称: (1R,5S)-6,6-Dimethyl-bicyclo[3.1.1]heptan-2-one oxime
• CAS: 90582-67-5
• 化学式: C₉H₁₅NO
• 分子量: 153.224
• InChiKey: RSECWFBXDMGUCL-BQBZGAKWSA-N

物化性质

• 沸点：
  241.6±9.0 °C(Predicted)
• 密度：
  1.21±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.27
• 重原子数：
  11.0
• 可旋转键数：
  0.0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.89
• 拓扑面积：
  32.59
• 氢给体数：
  1.0
• 氢受体数：
  2.0

反应信息

• 作为反应物：
  描述：

  (1R,5S)-6,6-Dimethyl-bicyclo[3.1.1]heptan-2-one oxime 在 bis(triphenylphosphine)nickel(II) chloride 三甲基氯硅烷 、 四甲基碘化铵 、 铁粉 、 间氯过氧苯甲酸 、 锌 、 三氯氧磷 作用下， 以 四氢呋喃 、 二氯甲烷 、 N,N-二甲基甲酰胺 为溶剂， 反应 106.0h， 生成 (S,6R,6'R,8R,8'R)-(-)-5,5',6,6',7,7',8,8'-octahydro-3,3',7,7,7',7'-hexamethylbi(6,8-methanoquinolin-2-yl)-1-oxide
  参考文献：
  名称：

  New Lewis-Basic N-Oxides as Chiral Organocatalysts in Asymmetric Allylation of Aldehydes

  摘要：

  Allylation of aromatic and heteroaromatic aldehydes 1a-k with allyltrichlorosilane 2 can be catalyzed by the new heterobidentate, terpene-derived bipyridine N-monoxides 4, 6a,b, and 8-11 (less than or equal to 10 mol %) to afford (S)-(-)-3 with high enantioselectivities (less than or equal to99% ee). The stereochemical outcome has been found to be controlled by the axial chirality of the catalyst, which in turn is determined by the central chirality of the annulated terpene units. Solvent effects on the conversion and the level of asymmetric induction have been elucidated, and MeCN has been identified as the optimal solvent for these catalysts.

  DOI：

  10.1021/jo035074i
• 作为产物：
  描述：

  (1R)-(+)-诺蒎酮 在 ammonium hydroxide hydrochloride 、 碳酸氢钠 作用下， 以 甲醇 、 水 为溶剂， 生成 (1R,5S)-6,6-Dimethyl-bicyclo[3.1.1]heptan-2-one oxime
  参考文献：
  名称：

  通过a烯衍生的内酰胺的阴离子聚合实现可持续的萜烯基聚酰胺

  摘要：

  衍生自可再生萜烯β-pine烯的可持续内酰胺通过便利的阴离子开环聚合（ROP）转化为聚酰胺，无需使用昂贵的催化剂即可轻松处理。所得聚酰胺具有良好的热性能，使其能够将来用作高性能聚合物。

  DOI：

  10.1039/c7cc08266e

文献信息

• CHIRALITY TRANSFER DURING CYCLOBUTYL–CYCLOPROPYLMETHYL–HOMOALLYL CATION REARRANGEMENT AND SYNTHESIS OF (−)-ELDANOLIDE
  作者：Yasushi Yokoyama、Masatoshi Yunokihara

  DOI：10.1246/cl.1983.1245

  日期：1983.8.5

  The (3R)-2,2-dimethyl-3-(2-methoxycarbonyl)ethylcyclobutyl cation rearranged to give (1S,2S)-1-(1-methoxy-1-methyl)ethyl-2-(2-methoxycarbonyl)ethylcyclopropane. The latter was transformed into (4R)-4-(3-methylbut-2-enyl)-4-butyrolactone with a high degree of chirality transfer. The γ-lactone was converted into (−)-eldanolide, an antipode of the wing gland pheromone of an African sugar-cane borer.

  (3R)-2,2-二甲基-3-(2-甲氧羰基)乙基环丁基阳离子重新排列后得到 (1S,2S)-1-(1-甲氧基-1-甲基)乙基-2-(2-甲氧羰基)乙基环丙烷。后者转化为(4R)-4-(3-甲基丁-2-烯基)-4-丁内酯，手性转移程度很高。γ-内酯被转化成(-)-eldanolide，这是一种非洲甘蔗螟虫翅腺信息素的反式。
• PINDY:  A Novel, Pinene-Derived Bipyridine Ligand and Its Application in Asymmetric, Copper(I)-Catalyzed Allylic Oxidation
  作者：Andrei V. Malkov、Marco Bella、Vratislav Langer、Pavel Kočovský

  DOI：10.1021/ol006111k

  日期：2000.10.1

  [GRAPHICS]The title bipyridine ligand (+)-6(PINDY), prepared in five steps from (-)-beta-pinene, forms a stable complex with CuCl2 (8) that has been characterized by X-ray crystallography to reveal an unusual geometry at Cu. Triflate 9 proved to catalyze asymmetric allylic oxidation (10 --> 11; rt, similar to 30 min, 49-75% ee).
• Natural terpene-based derivatives to control postharvest sclerotinia rot and the involved potential mechanism
  作者：Jiuhui Ye、Xin Liu、Rui Zhou、Tuoping Hui、Jian Li、Juntao Feng、Zhiqing Ma、Yanqing Gao

  DOI：10.1016/j.ijfoodmicro.2023.110461

  日期：2024.1