(1R,5R)-6,6-dimethyl-3-methylenebicyclo[3.1.1]heptan-2-one | 34413-89-3

• 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,5R)-6,6-dimethyl-3-methylenebicyclo[3.1.1]heptan-2-one
• 英文别名: (1R,5R)-6,6-Dimethyl-3-methylene-bicyclo[3.1.1]heptan-2-one；(1R,5R)-6,6-dimethyl-3-methylidenebicyclo[3.1.1]heptan-2-one
• CAS: 34413-89-3
• 化学式: C₁₀H₁₄O
• 分子量: 150.221
• InChiKey: CRJCHFGJXXBNDS-YUMQZZPRSA-N

物化性质

• 熔点：
  72 °C
• 沸点：
  37-40 °C(Press: 0.1 Torr)
• 密度：
  0.99±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.2
• 重原子数：
  11
• 可旋转键数：
  0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.7
• 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：

  (1R,5R)-6,6-dimethyl-3-methylenebicyclo[3.1.1]heptan-2-one 在 臭氧 、 二甲基硫 作用下， 以 二氯甲烷 为溶剂， 以70%的产率得到(1R,5R)-6,6-dimethylbicyclo[3.1.1]heptane-2,3-dione
  参考文献：
  名称：

  Utilizing terpene derivatives in the synthesis of annulated terpene-imidazoles with application in the nitroaldol reaction

  摘要：

  Two classes of terpene derivatives (diketones and monoximes) were condensed into annulated terpeneimidazoles using two general methods. Method A, involving the condensation of terpene diketones and aldehydes, gave lower yields than Method B, which employed terpene monoximes and amines. The mechanism of Method B is discussed. Using both methods, overall 11 new imidazole ligands were synthesized and fully characterized. The molecular structures of the side product 16 and intermediate 4b were also characterized by X-ray analysis. Regarding la, N-methylation and subsequent ortho-lithiation and quenching with diphenylphosphinechloride were proven. The synthesized ligands were tested in the Henry reaction providing reaction times 24-72 h and enantioselectivities up to 32% especially for the pyridine 2-substituted ligands 1c, 2c, 3b and N,P-ligand 17. (C) 2008 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetasy.2008.10.026
• 作为产物：
  描述：

  beta-pinene 在 四氧化锇 、 聚合甲醛 、 十二/十四烷基二甲基氧化胺 、 sodium carbonate 、 sodium amide 作用下， 以 叔丁醇 、 苯 为溶剂， 反应 21.67h， 生成 (1R,5R)-6,6-dimethyl-3-methylenebicyclo[3.1.1]heptan-2-one
  参考文献：
  名称：

  从天然存在的单萜合成手性​​ C2-对称 1,10-菲咯啉

  摘要：

  报道了一种制备手性 C 2 -对称 1,10-菲咯啉的简便方法，该手性骨架在杂环的 2,3-和 8,9-位上具有环烯缩合取代基形式的手性骨架。以 2-苄氧基环己酮为原料，根据基于方法的方法制备了四种衍生自 (-)-β-蒎烯、(+)-α-蒎烯、(-)-异松香酚和 (+)-樟脑的 1,10-菲咯啉在双迈克尔 - 氮杂环化 - 芳香化序列上。

  DOI：

  10.1055/s-2003-36260

文献信息

• APOPTOSIS-INDUCING AGENTS FOR THE TREATMENT OF CANCER AND IMMUNE AND AUTOIMMUNE DISEASES
  申请人：Ding Hong

  公开号：US20110237553A1

  公开（公告）日：2011-09-29

  Disclosed are compounds which inhibit the activity of anti-apoptotic Bcl-2 proteins, compositions containing the compounds and methods of treating diseases during which is expressed anti-apoptotic Bcl-2 protein.

  揭示了抑制抗凋亡Bcl-2蛋白活性的化合物，包含这些化合物的组合物以及治疗在其中表达抗凋亡Bcl-2蛋白的疾病的方法。
• Enantioselective Mukaiyama-Michael Reaction Catalyzed by a Chiral Rhodium Complex Based on Pinene-Modified Pyridine Ligands
  作者：Jun Gong、Qian Wan、Qiang Kang

  DOI：10.1002/asia.201800318

  日期：2018.9.4

  rhodium complex Λ‐Rh1 containing chiral pinene‐modified pyridine ligands is prepared through a two‐step synthetic procedure; it exhibits excellent reactivity and enantiocontrol towards the enantioselective Mukaiyama–Michael reaction of α,β‐unsaturated 2‐acyl imidazoles with silyl enol ethers, affording enantioenriched 1,5‐dicarbonyl compounds in good yields (up to 99 %) with excellent enantioselectivities

  含有手性complex烯修饰的吡啶配体的铑配合物 Λ-Rh1是通过两步合成程序制备的；它对α，β-不饱和2-酰基咪唑与甲硅烷基烯醇醚的对映选择性Mukaiyama-Michael反应表现出优异的反应性和对映体控制性能，可提供高收率（高达99％）的对映体富集的1,5-二羰基化合物，并具有出色的对映选择性（高达到99％ee）。
• Platinum(II) Compounds with Enantiomerically Pure Bis(pinene)-Fused Bipyridine Ligands − Diimine-Dichloro Complexes and Their Substitution Reactions
  作者：Brunhilde Kolp、Dirk Abeln、Helen Stoeckli-Evans、Alexander von Zelewsky

  DOI：10.1002/1099-0682(200105)2001:5<1207::aid-ejic1207>3.0.co;2-4

  日期：2001.5

  The synthesis of chiral square-planar PtII complexes using symmetrical and unsymmetrical bis(pinene)-fused 2,2′-bipyridine is described. The neutral diimine dichloro complexes show a strong deviation of the coordination sphere from planarity if the pinene groups are attached at the 5- and 6-positions of the pyridine rings. However, this distortion does not occur in parallel with the chiral configuration

  描述了使用对称和不对称双 (蒎烯)-稠合 2,2'-联吡啶合成手性方形平面 PtII 复合物。如果蒎烯基团连接在吡啶环的 5 位和 6 位，则中性二亚胺二氯配合物显示出配位球与平面性的强烈偏差。然而，这种扭曲不会与二亚胺配体的手性构型同时发生。当使用手性二胺的外消旋混合物时，用二胺取代两个顺氯配体形成五元螯合环显示出很小的非对映选择性。此外，在连接中心是前手性的配体在配位时几乎没有选择性。
• Syntheses of C1-symmetric bidentate ligands having pyridyl and 1,3-Thiazolyl, 1-methylimidazolyl or pyrazinyl donor groups for enantioselective palladium-catalyzed allylic substitution and copper-catalyzed cyclopropanation
  作者：Pang-Fei Teng、Chui-Shan Tsang、Ho-Lun Yeung、Wing-Leung Wong、Wing-Tak Wong、Hoi-Lun Kwong

  DOI：10.1016/j.jorganchem.2006.06.050

  日期：2006.12

  New chiral C1-symmetric bidentate ligands, which possess two different nitrogen heterocycles, 1,3-thiazolyl, 1-methylimidazolyl or pyrazinyl and one pyridyl group, were prepared by Kröhnke condensation in 36–59% overall yield. Stable Pd(II)-allyl and Cu(II) chloride complexes formed by some of the ligands were obtained in 60–65% yields. X-ray crystal structure analysis of a copper(II) complex having

  通过Kröhnke缩合反应制备了具有2个不同的氮杂环，1,3-噻唑基，1-甲基咪唑基或吡嗪基和一个吡啶基的新的手性C 1对称双齿配体，总收率为36-59％。由某些配体形成的稳定的Pd（II）-烯丙基和Cu（II）氯化物络合物的收率为60-65％。具有1-甲基咪唑基的铜（II）配合物的X射线晶体结构分析表明它是μ-氯桥二聚体。发现Pd（II）-烯丙基络合物是乙酸1，3-二苯基丙-2-烯基酯的不对称烯丙基取代中的活性催化剂。观察到的最佳结果是85％ee和99％分离产率。另外，原位生成Cu（OTf）2 发现该配合物是苯乙烯与重氮乙酸乙酯进行环丙烷化的活性催化剂。
• Metallo-macrocycles with labile coordination sites through self assembly: Binuclear phenyl bridged bisbipyridine manganese complexes
  作者：Kiu-Chor Sham、Guoli Zheng、Yinyan Li、Shek-Man Yiu、Hoi-Lun Kwong

  DOI：10.1039/c1dt11589h

  日期：——

  Self assembly of phenyl bridged bisbipyridines with manganese perchlorate gave structurally different metallo-macrocycles having cis-labile coordination sites which can catalyse olefin epoxidation with peracetic acid in good yield.

  苯桥接的双皮啶与高氯酸锰的自组装生成了结构不同的金属大环，具有顺式可离解的配位位点，能够在与过氧乙酸的反应中高效催化烯烃环氧化反应。