(+)-7,7-dimethyl-1-vinyl-2-norbornanone | 53585-70-9

• 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: (+)-7,7-dimethyl-1-vinyl-2-norbornanone
• 英文别名: (1S)-2-oxo-7,7-dimethyl-1-vinylbicyclo<2.2.1>heptane；D-2-oxo-7,7-dimethyl-1-vinylbicyclo<2.2.1>heptane；(1S,4R)-7,7-dimethyl-1-vinylbicyclo[2.2.1]heptan-2-one；7,7-dimethyl-1-vinylbicyclo[2.2.1]heptan-2-one；(1S)-7,7-dimethyl-1-vinyl-2-norbornanone；7,7-dimethyl-1-vinylnorbornan-2-one；Bicyclo[2.2.1]heptan-2-one, 1-ethenyl-7,7-dimethyl-, (1S,4R)-；(1S,4R)-1-ethenyl-7,7-dimethylbicyclo[2.2.1]heptan-2-one
• CAS: 53585-70-9
• 化学式: C₁₁H₁₆O
• 分子量: 164.247
• InChiKey: UEVFTEJYOXJPNL-KCJUWKMLSA-N

物化性质

• 沸点：
  212.3±19.0 °C(Predicted)
• 密度：
  1.054±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.5
• 重原子数：
  12
• 可旋转键数：
  1
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.73
• 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：

  (+)-7,7-dimethyl-1-vinyl-2-norbornanone 在 二甲基硫 、 臭氧 作用下， 生成 7,7-Dimethyl-2-oxobicyclo[2.2.1]heptane-1-carbaldehyde
  参考文献：
  名称：

  A means for stereocontrolled introduction of the C-2 oxygen substituent in functionalized cis-tricyclo[9.3.1.03,8]pentadecanones related to taxol

  摘要：

  Several optically pure cis-tricyclo[9.3.1.0(3,8)]pentadecanones have been prepared via anionic oxy-Cope rearrangement of exo-norbornanol precursors that have been obtained by convergent coupling of two functionalized reaction partners. The sigmatropic rearrangement is shown to proceed with exceptionally good stereochemical transmission because of universal adherence to the same endo-chair transition state. The atropisomeric aspects of this pivotal transformation are addressed. Also investigated was the proclivity of the products to undergo transannular hemiketal formation following osmylation of the bridgehead double bond. As matters turn out, the operation or nonoperation of this intramolecular addition to the C-9 carbonyl group is amenable to control merely by adjusting properly the stereochemistry of a single pendant substituent.

  DOI：

  10.1021/jo00076a058
• 作为产物：
  描述：

  生成 (+)-7,7-dimethyl-1-vinyl-2-norbornanone
  参考文献：
  名称：

  Kempe,T.; Norin,T., Acta Chemica Scandinavica (1947), 1973, vol. 27, p. 1452

  摘要：

  DOI：

文献信息

• Camphor-derived alcohols: An anomalous reaction of 3-hydroxycamphor and the influence of internal alkoxides on the alkylation stereochemistry of glycinate imines
  作者：John M. McIntosh、Kenneth C. Cassidy、Luca C. Matassa

  DOI：10.1016/s0040-4020(01)89491-6

  日期：1989.1

  Attempted imine formation between 3-hydroxycamphor and tert. butyl glycinate led to 8 the substitution product at the 3-position. Zinc-acetic acid treatment of 8 afforded 3-acetoxycamphor. Alkylation of the imine from from norcamphor and tert. butyl glycinate gave no stereoselection. Alkylation of the imine from from 10-hytdroxymethylcamphor and tert. butyl glycinate gave stereoselectivities inferior

  尝试在3-羟基樟脑和叔胺之间形成亚胺。甘氨酸丁酸丁酯在3位上产生8个取代产物。锌-乙酸处理8得到3-乙酰氧基樟脑。来自正樟脑和叔胺的亚胺烷基化。甘氨酸丁酯没有给出立体选择。来自10-羟基甲基樟脑和叔胺的亚胺烷基化。甘氨酸丁酸丁酯的立体选择性不如樟脑亚胺（1），但醛醇与苯甲醛的缩合反应（1不可能发生），收率高达71％。
• Synthesis of ent-herbasolide
  作者：Tse-Lok Ho、Fu-Sen Liang

  DOI：10.1039/cc9960001887

  日期：——

  ent-Herbasolide is synthesised by elaboration of (+)-10-camphorsulfonyl chloride which involves homologation at C-10, cleavage of the C-2/C-3 bond, oxidation at C-5 and chain extension at C-3 of the camphor skeleton.

  ent-Herbasolide 是通过对(+)-10-樟脑磺酰氯的详细化合成的，其中涉及在C-10处的同系物化、C-2/C-3键的断裂、C-5的氧化以及在樟脑骨架的C-3处的链延伸。
• High-Rate Accelerations in Oxy-Cope Rearrangements Induced by Sulfur Substitution:  Kinetic Study Involving Electronically and Geometrically Differentiated 1-Alkenyl-2-(<i>Z</i>-1-propenyl)-7,7-dimethyl-<i>exo</i>-norbornan-2-ols
  作者：Leo A. Paquette、Y. Ravindra Reddy、Grigoriy Vayner、K. N. Houk

  DOI：10.1021/ja0025402

  日期：2000.11.1

  carbon of the bridgehead vinyl group and the geometric nature of the olefinic center. The results convincingly establish that although an OPMP substituent exerts, at best, a very modest decelerative kinetic effect, the presence of the PhS substituent causes rearrangement to occur approximately 103 times faster by lowering the activation energy to the extent of 3−4 kcal/mol. This remarkable divergence

  已经确定了五种结构相关的外降冰片醇的阴离子促进的氧-科普重排率。这些底物的取代模式的一个关键区别是桥头乙烯基末端碳上是否存在氧或硫官能团以及烯烃中心的几何性质。结果令人信服地证明，尽管 OPMP 取代基最多发挥非常温和的减速动力学效应，但 PhS 取代基的存在通过将活化能降低至 3-4 kcal/mol 的程度，使重排发生速度提高约 103 倍. 这种显着的行为差异被证明与计算预测的过渡态的高度解离性质密切相关。
• ——
  作者：N. S. Vostrikov、A. V. Abutkov、V. Z. Vasikov、M. S. Miftakhov

  DOI：10.1023/a:1026048910542

  日期：——

  (1S,4R)-7,7-Dimethyl-1-vinylbicyclo[2.2.1]heptan-2-one oxime in the system (CF3CO)(2)O- CF3COOH and (1S,4R)-1-(1,2-dibromoethyl)-7,7-dimethylbicyclo[2.2.1]heptan-2-one in the system MeONa-MeOH undergo fragmentation to give exo-alkylidenecyclopentane derivatives, (4R)-4-cyanomethyl-5,5-dimethyl-1-[(1E)-trifluoroacetoxyethylidene]cyclopentane and isomeric (4R)-4-carboxymethyl-1-[(1ZE)-2-methoxyethylidene]-5,5-dimethylcyclopentanes, respectively. The trifluoroacetate derivative undergoes unusual rearrangement, yielding an equilibrium mixture of two isomers with endo- and exocyclic double bond.

  在系统(CF3CO)2O-CF3COOH中，(1S,4R)-7,7-二甲基-1-乙烯基双环[2.2.1]庚-2-酮肟发生断裂，生成外环丙烯基环戊烷衍生物，即(4R)-4-氰甲基-5,5-二甲基-1-[(1E)-三氟乙酸乙氧基乙烯基]环戊烷。在系统MeONa-MeOH中，(1S,4R)-1-(1,2-二溴乙基)-7,7-二甲基双环[2.2.1]庚-2-酮发生断裂，生成(4R)-4-羧甲基-1-[(1Z)-2-甲氧基乙烯基]-5,5-二甲基环戊烷及其异构体。三氟乙酸酯衍生物会发生不寻常的重排，生成两种具有环内和环外双键的异构体的平衡混合物。
• Chiral Polysiloxane‐Fixed Metal 1,3‐Diketonates (Chirasil‐Metals) as Catalytic Lewis Acids for a Hetero Diels‐Alder Reaction ‐Inversion of Enantioselectivity Upon Catalyst ‐Polymer Binding
  作者：Fritz Keller、Hilmar Weinmann、Volker Schurig

  DOI：10.1002/cber.19971300711

  日期：1997.7

  Lewis acid catalyst (1R)-(+)-oxovanadium(1V) bis[3- heptafluorobutanoylcamphorate] [(+)-5a] at the C-10 position of the camphor moiety yielding the novel chiral polymeric (1S)-( +)-oxovanadium(1V) bis[3-heptafluorobutanoylcamphorate] -dimethylpolysiloxane [( +)-6a][1]. The Lewis acid promoted hetero Diels-Alder reaction of trans-l-methoxy-3-(trimethylsilyloxy)- 1,3-butadiene (1) and benzaldehyde (2) is

  二甲基聚硅氧烷链在樟脑部分的C-10位置共价键合到单体路易斯酸催化剂（1R）-（+）-氧钒（1V）双[3-七氟丁酸酰基樟脑酸酯] [（+）- 5a ]手性聚合物（1S）-（+）-氧钒（1V）双[3-七氟丁酸酰基樟脑酸酯]-二甲基聚硅氧烷[（+）- 6a ] [1]。在对映体纯单体（5a，5b）存在下，研究了Lewis酸促进的反式-甲氧-3-（三甲基甲硅烷氧基）-1,3-丁二烯（1）和苯甲醛（2）的杂Diels-Alder反应。和聚合物（6a，6b）催化剂。手性相同的单体和聚合催化剂[1]对形成2-苯基-2，3-二氢-4H-吡喃酮具有相反的对映选择性（4）。众多对照实验证实了这一非凡的结果。因此，证明了当络合物固定到聚合物链上时，催化剂的活性位点的环境改变了。与5和6相反，具有相同手性的单体12和聚合物13（（III）三[3-七氟丁酰基樟脑草酸酯]对4的形成具有相同的对映选择性。利用聚合物附