(1R,4S,5R)-4,6,6-trimethyl-2-methylenebicyclo[3.1.1]heptan-3-one | 409319-24-0

• 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,4S,5R)-4,6,6-trimethyl-2-methylenebicyclo[3.1.1]heptan-3-one
• 英文别名: (1R,2S,5R)-2,6,6-trimethyl-4-methylenebicyclo[3.1.1]heptan-3-one；(1R,2S,5R)-2,6,6-trimethyl-4-methylidenebicyclo[3.1.1]heptan-3-one
• CAS: 409319-24-0
• 化学式: C₁₁H₁₆O
• 分子量: 164.247
• InChiKey: RZNAKUUCNJACII-XHNCKOQMSA-N

物化性质

• 沸点：
  229.2±7.0 °C(Predicted)
• 密度：
  0.98±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.7
• 重原子数：
  12
• 可旋转键数：
  0
• 环数：
  3.0
• 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：

  (1R,4S,5R)-4,6,6-trimethyl-2-methylenebicyclo[3.1.1]heptan-3-one 在 ammonium acetate 、 三苯基膦 、 nickel dichloride 、 锌 作用下， 以 溶剂黄146 、 N,N-二甲基甲酰胺 为溶剂， 反应 6.0h， 生成 (1R,8S,9R)-8,10,10-trimethyl-5-[6-[6-[(1R,8S,9R)-8,10,10-trimethyl-6-azatricyclo[7.1.1.02,7]undeca-2(7),3,5-trien-5-yl]pyridin-2-yl]pyridin-2-yl]-6-azatricyclo[7.1.1.02,7]undeca-2(7),3,5-triene
  参考文献：
  名称：

  Stereoselective formation of a single-stranded helicate: Structure of a bis(palladium-allyl)quaterpyridine complex and its use in catalytic enantioselective allylic substitution

  摘要：

  手性 C2 对称四吡啶 L 与[Pd(η3-C3H5)Cl]2 反应生成手性单链螺旋双核钯配合物[Pd2(η3-C3H5)2(L)]2+；该配合物能有效催化 1,3-二苯基丙-2-烯基乙酸酯与丙二酸二甲酯的烯丙基取代反应，对映选择性高达 85%。

  DOI：

  10.1039/b608481h
• 作为产物：
  描述：

  (-)-异松蒎醇 在 chromium(VI) oxide 、 聚合甲醛 、 硫酸 、 sodium ethanolate 、 potassium carbonate 作用下， 以 乙醚 、 乙醇 、 丙酮 为溶剂， 反应 15.83h， 生成 (1R,4S,5R)-4,6,6-trimethyl-2-methylenebicyclo[3.1.1]heptan-3-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

• 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。
• Design of a new class of chiral C 2 -symmetric dipyridylmethane ligands and their application in asymmetric catalysis
  作者：Giorgio Chelucci、Giovanni Loriga、Gabriele Murineddu、Gerard A. Pinna

  DOI：10.1016/s0040-4039(02)02066-x

  日期：2002.11

  A new class of chiral C2-symmetric dipyridylmethane ligands was prepared from naturally occurring monoterpenes, according to a method based on a double Michael–azaannellation–aromatization sequence. These ligands were assessed in the enantioselective palladium-catalyzed allylic alkylation of 1,3-diphenylprop-2-enyl acetate with dimethylmalonate and in the copper-catalyzed cyclopropanation of styrene

  根据基于双迈克尔-氮杂退火-芳构化序列的方法，从天然单萜中制备了一类新的手性C 2对称二吡啶基甲烷配体。这些配体在1，3-二苯基丙-2-烯基乙酸酯与丙二酸二甲酯的对映选择性钯催化的烯丙基烷基化反应中以及在苯乙烯与重氮乙酸乙酯的铜催化的环丙烷化中评价这些配体。获得高达88％ee的对映选择性。
• Chiral C1-symmetric 2,2′:6′,2′′-terpyridine ligands: Synthesis, characterization, complexation with copper(II), rhodium(III) and ruthenium(II) ions and use of the complexes in catalytic cyclopropanation of styrene
  作者：Chi-Tung Yeung、Wing-Sze Lee、Chui-Shan Tsang、Shek-Man Yiu、Wing-Tak Wong、Wai-Yeung Wong、Hoi-Lun Kwong

  DOI：10.1016/j.poly.2010.01.017

  日期：2010.3

  copper(II) complexes, of formula [Cu(L)Cl2], the rhodium(III) complexes, of formula [Rh(L)Cl3], and the ruthenium(II) complexes, of formula cis- or trans-[Ru(L)(X)Cl2] (X = DMSO or CO), were synthesized. Structures of a chiral C1-ligand, a copper complex, a rhodium complex and a ruthenium DMSO complex were analysed using X-ray crystal structure analysis. The copper, rhodium and ruthenium complexes were

  摘要制备了三个新的光学纯的C1-吡啶配体（L1-3），式[Cu（L）Cl2]的铜（II）配合物，式[Rh（L）Cl3]的铑（III）配合物，并合成了具有顺式或反式[Ru（L）（X）Cl2]（X = DMSO或CO）的钌（II）配合物。使用X射线晶体结构分析来分析手性C 1配体，铜配合物，铑配合物和钌DMSO配合物的结构。铜，铑和钌配合物被证明是环丙烷化催化剂的前体。[Cu（L）Cl2]，[Rh（L）Cl3]或顺式或反式[Ru（L）（X）Cl2]与AgOTf的反应将络合物转化为催化剂，在反式[Ru]的情况下（L）（CO）Cl2]对苯乙烯环丙烷与重氮乙酸叔丁酯的顺式异构体的对映选择性高达67％ee。与铜的C2-类似物的比较，
• Single-, double- and triple-stranded helical metal complexes of chiral tetradentate pyridyl-thiazole ligands: Stereoselective synthesis, spectroscopic properties and structural characterization
  作者：Chui-Shan Tsang、Chi-Chung Yee、Shek-Man Yiu、Wing-Tak Wong、Hoi-Lun Kwong

  DOI：10.1016/j.poly.2014.05.062

  日期：2014.11

  With a series of chiral pyridine-based tetradentate pyridyl-thiazole ligands L, three types of binuclear helical metal complexes were synthesized. They were the Re(I) single-stranded complexes of formula [Re-2(L)(CO)(6)Br-2], the Ag(I) double-stranded complexes of formula [Ag-2(L)(2)](ClO4)(2) and the Cu(II) triple-stranded complex of formula [Cu-2(L)(3)](ClO4)(4). Each type of them has been characterized using CD spectroscopy and if possible H-1 NMR spectroscopy. Three single crystal structures, one from each type, have been determined. (C) 2014 Elsevier Ltd. All rights reserved.
• Chiral pyridine N-oxides derived from monoterpenes as organocatalysts for stereoselective reactions with allyltrichlorosilane and tetrachlorosilane
  作者：Giorgio Chelucci、Salvatore Baldino、Gerard A. Pinna、Maurizio Benaglia、Laura Buffa、Stefania Guizzetti

  DOI：10.1016/j.tet.2008.05.105

  日期：2008.8

  The synthesis of enantiomerically pure C-2-symmetric dipyridylmethane ligands and related N,N'-dioxides is reported. A procedure for the synthesis of a few new enantiomerically pure C-2-symmetric pyridine N-oxides and the preparation of four pyridine N-oxides with oxygen and nitrogen atoms as further coordinating elements in the heterocycle framework is described. All compounds were prepared from naturally occurring monoterpenes. These new compounds were assessed as organocatalysts in two different reactions, namely the allylation of aldehydes with allyltrichlorosilane that afforded homoallylic alcohols in good yields and up to 85% ee and the stilbene oxide opening by the addition of tetrachlorosilane that gave chlorohydrin in quantitative yield and up to 70% ee. (C) 2008 Elsevier Ltd. All rights reserved.