(1R,4E,5S)-4-[(dimethylamino)methylidene]-1,8,8-trimethyl-2-oxabicyclo[3.2.1]octan-3-one | 769133-62-2

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 内酯类
• 英文名称: (1R,4E,5S)-4-[(dimethylamino)methylidene]-1,8,8-trimethyl-2-oxabicyclo[3.2.1]octan-3-one
• 英文别名: (1R,5S)-4-[(E)-(dimethylamino)methylidene]-1,8,8-trimethyl-2-oxabicyclo[3.2.1]octan-3-one；(1R,4E,5S)-4-(dimethylaminomethylidene)-1,8,8-trimethyl-2-oxabicyclo[3.2.1]octan-3-one
• CAS: 769133-62-2
• 化学式: C₁₃H₂₁NO₂
• 分子量: 223.315
• InChiKey: QKQUCYATXASDST-NNWFXZMQSA-N

物化性质

• 沸点：
  323.2±25.0 °C(Predicted)
• 密度：
  1.091±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.2
• 重原子数：
  16
• 可旋转键数：
  1
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.77
• 拓扑面积：
  29.5
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  (1R,4E,5S)-4-[(dimethylamino)methylidene]-1,8,8-trimethyl-2-oxabicyclo[3.2.1]octan-3-one 在 盐酸肼 作用下， 以 丙醇 为溶剂， 反应 5.0h， 以83%的产率得到4-[(1S,3R)-3-hydroxy-2,2,3-trimethylcyclopentyl]-1H-pyrazol-3-ol
  参考文献：
  名称：

  Cyclocondensations of (+)-camphor derived enaminones with hydrazine derivatives

  摘要：

  Reactions of 3-[(E)-(dimethylamino)methylidene]-(+)-camphor and (1R,5S)-4-[(E)-(dimethylamino)methylidene]-1,8,8-trimethyl-2-oxabicyclo[3.2.1]octan-3-one with hydrazine derivatives were studied. Treatment of 3-[(E)-(dimethylamino)methylidene]-(+)camphor with hydrazines afforded the corresponding fused pyrazoles. Similarly, fused pyrazoles were obtained upon reaction of (1R,5S)-4-[(E)-(dimethylamino)methylidene]-1,8,8-tritnethyl-2-oxabicyclo[3.2.1]octan-3-one with ortho-unsubstituted phenylhydrazines, while reactions with ortho-substituted phenylhydrazines and with hydrazine hydrochloride resulted in 'ring switching' type of transformation to furnish 2-aryl-4-[(1S, 3R)-3-hydroxy-2,2,3-trimethylcyclopentyl]-1,2-dihydro-3H-pyrazol-3-ones. (c) 2005 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tet.2005.02.048
• 作为产物：
  描述：

  Bredereck 试剂 、 1,8,8-trimethyl-2-oxabicyclo<3.2.1>octan-3-one 以 N,N-二甲基甲酰胺 为溶剂， 生成 (1R,4E,5S)-4-[(dimethylamino)methylidene]-1,8,8-trimethyl-2-oxabicyclo[3.2.1]octan-3-one
  参考文献：
  名称：

  含哒嗪及其相关部分的功能化化合物的合成

  摘要：

  3-氨基哒嗪17和3-肼基哒嗪18被用作制备各种类型的官能化的含哒嗪环的化合物的基础。3-氨基哒嗪用于合成3-（6-氯咪唑并[1,2- b ]哒嗪-2-基）丙氨酸26、27，并用于制备3-氨基-4 H-嘧啶基[1,2- b ]哒嗪-4-酮103，中间体烷基1-哒嗪-3-基- 1,2,3-三唑-4-羧酸盐的“环切换”合成106。另一方面，hydrazinopyridazines 18是在采用两步制备3-官能化的1,2,4-三唑[4,3- b通过与官能化醛及其烯胺类似物缩合，然后氧化中间体进行氧化环化而得到]哒嗪。以这种方式，1,2,4-三唑并[4,3- b ]哒嗪-3-基取代的丙氨酸29，30，多元醇33，39-48，Ç核苷49，50，和萜烯，58，62，64 –69准备好了。在另一种一般的方法，3- hydrazinopyridazines 18用官能化烯胺酮1,3- dielectrop

  DOI：

  10.1002/jhet.5570420303

文献信息

• Stereoselective additions to the exocyclic CC bond of some α-alkylidene-(+)-camphor derivatives
  作者：Uroš Grošelj、David Bevk、Renata Jakše、Anton Meden、Branko Stanovnik、Jurij Svete

  DOI：10.1016/j.tetasy.2006.04.014

  日期：2006.4

  Stereoselective additions to the exocyclic CC double bond of some (1R,3E,4S)-3-alkylidene-1,7,7-trimethylbicyclo[2.2.1]heptan-2-ones and (1R,4E,5S)-4-alkylidene-1,8,8-trimethyl-2-oxabicyclo[3.2.1]octan-3-ones were studied. All additions took place predominantly from the less hindered endo-face of the methylidene compounds to give the corresponding exo-adducts as the major isomers. Thus, catalytic hydrogenations

  一些（1 R，3 E，4 S）-3-亚烷基-1,7,7-三甲基双环[2.2.1]庚-2--2-和（1 R，4 E，研究了5 S）-4-亚烷基-1,8,8-三甲基-2-氧杂双环[3.2.1] octan-3-one。所有添加发生主要来自较少阻碍内的亚甲基化合物的-面，得到相应的外-adducts为主要异构体。因此，催化氢化提供了α-烷基化的（1 R，3 R，4 R）-1,7,7-三甲基双环[2.2.1]庚基-2-酮和（1 R，4 R，5R）-1,8,8-三甲基-2-氧杂双环[3.2.1] octan-3-ones in 28-100％de。同样，2,4,6-三取代的苄腈氧化物的1,3-偶极环加成反应生成相应的螺环加合物，其取代度为66-100％。通过2D NMR技术，NOESY光谱和X射线衍射确定了结构。
• Stereoselective Synthesis of (1<i>R</i>,5<i>S</i>)-4-[(<i>E</i>)-Alkylidene]-1,8,8-trimethyl-2-oxabicyclo[3.2.1]octan-3-ones
  作者：Jurij Svete、Uroš Grošelj、David Bevk、Renata Jakše、Anton Meden、Simon Rečnik、Branko Stanovnik

  DOI：10.1055/s-2005-861862

  日期：——

  Various (1R,5S)-4-[(E)-alkylidene]-1,8,8-trimethyl-2-oxabicyclo[3.2.1]octan-3-ones were prepared, stereoselectively, via coupling of (1R,5S)-4-[(E)-(dimethylamino)methylidene]-1,8,8-trimethyl-2-oxabicyclo[3.2.1]octan-3-one with Grignard reagents, potassium cyanide, and 2-methyl-1H-indole.

  通过 (1R,5S)-4-[(E)-亚烷基]-1,8,8-三甲基-2-氧杂二环[3.2.1]辛烷-3-酮的立体选择性偶联，制备了各种 (1R,5S)-4-[(E)-亚烷基]-1,8,8-trimethyl-2-oxbicyclo[3.2.1]octan-3-ones )-4-[(E)-(二甲基氨基)亚甲基]-1,8,8-三甲基-2-氧杂双环[3.2.1]辛烷-3-酮与格氏试剂、氰化钾和2-甲基-1H-吲哚。
• Synthesis and reductions of (1R,4E,5S)-4-oximino-1,8,8-trimethyl-2-oxabicyclo[3.2.1]octan-3-one
  作者：Uroš Grošelj、David Bevk、Renata Jakše、Anton Meden、Branko Stanovnik、Jurij Svete

  DOI：10.1016/j.tetasy.2005.04.026

  日期：2005.6

  (1R,4E, 5S)-4-Oximino-1,8,8-trimethyl-2-oxabicyclo[3.2.1]octan-3-one 9 was prepared in three steps from (1R)-(+)-camphor 1 via nitrosation of(1R,4E,5S)-4-[(diinetliylamino)methylidene]-1,8,8-trimethyl-2-oxabicyclo[3.2.1]octan-3-one 8. Catalytic hydrogenation of 9 under various reaction conditions afforded (1R,4S, 5S)-4-amino-1, 8,8-trimethyl-2-oxabicyclo[3.2.1]octan-3-one derivatives 11, 13, and 15b. On the other hand, reduction of 9 with Grignard reagents led to two types of products, (lR,4S,5S)4-dialkylamino-1,8,8-trimethyl-2-oxabicyclo[3.2.1]octan-3-ones 15b and 15c and/or 2-substituted (1E)-1-[(1S,3R)-3-hydroxy-2,2,3-trimethylcyclopentyllethane-1,2-dione 1-oximes 16a,b and 15d-f. The structures of compounds 9, 10' 15b, and 16b were determined by X-ray diffraction. (c) 2005 Elsevier Ltd. All rights reserved.

  (1R,4E,5S)-4-氧亚胺基-1,8,8-三甲基-2-氧杂双环[3.2.1]辛-3-酮 9 是通过三步反应从 (1R)-(+)-樟脑 1 开始合成的，其中关键步骤是(1R,4E,5S)-4-[(二甲基亚氨基)亚甲基]-1,8,8-三甲基-2-氧杂双环[3.2.1]辛-3-酮 8 的亚硝化反应。在不同的反应条件下，对 9 进行催化解氢还原，得到 (1R,4S,5S)-4-氨基-1,8,8-三甲基-2-氧杂双环[3.2.1]辛-3-酮衍生物 11、13 和 15b。另一方面，以 Grignard 试剂对 9 进行还原反应，得到了两种类型的产品，分别为 (1R,4S,5S)-4-双烷基氨基-1,8,8-三甲基-2-氧杂双环[3.2.1]辛-3-酮 15b 和 15c，以及 2-取代的 (1E)-1-[(1S,3R)-3-羟基-2,2,3-三甲基环戊基]乙烷-1,2-二酮-1-亚胺 16a、b 和 15d-f。化合物 9、10'、15b 和 16b 的结构通过 X 射线衍射确定。© 2005 Elsevier Ltd. 保留所有权利。
• Synthesis and transformations of new dihydro-β-campholenolactone derivatives
  作者：Uroš Grošelj、Gašper Tavčar、David Bevk、Anton Meden、Boris Žemva、Branko Stanovnik、Jurij Svete

  DOI：10.1016/j.tetasy.2006.06.007

  日期：2006.7

  The reaction of xenon difluoride with enamino lactone 3 furnished the new alpha-fluoro aldehyde 7, whereas reaction of 3 with anhydrous HF led to racemic dihydro-beta-campholenolactone 6. Acid-catalysed rearrangement of alpha-ethylidenclactone 4 proceeded with retention of configuration to give beta-campholenolactone 8. Nitrosation of the novel bicyclic enamino lactone 6 afforded the corresponding oxime 9, while acid-catalysed treatment with primary amines, 2-methyl-1H-indole, potassium cyanide and hydrazine hydrochloride, furnished the dimethylamine substitution products 11-13 and the 'ring switched' product 14. The structures were determined by 2D NMR techniques, NOESY spectroscopy and X-ray diffraction. (c) 2006 Elsevier Ltd. All rights reserved.
• Synthesis and properties of N-substituted (1R,5S)-4-aminomethylidene-1,8,8-trimethyl-2-oxabicyclo[3.2.1]octan-2-ones
  作者：Uroš Grošelj、David Bevk、Renata Jakše、Anton Meden、Samo Pirc、Simon Rečnik、Branko Stanovnik、Jurij Svete

  DOI：10.1016/j.tetasy.2004.06.008

  日期：2004.8

  N-Substituted (1R,5S)-4-aminomethylidene-1,8,8-trimethyl-2-oxabicyclo[3.2.1]octan-3-ones were prepared in three steps from (1R)-(+)-camphor via coupling of (2R,4E, 5S)-3-[(dimethylamino)methylidene]- 1, 8,8-trimethyl-2-oxabicyclo[3.2.1] octan-3-one with primary amines. N,N'-Bis-[(1R,5S)-1,8,8-trimethyl-3-oxo-2-oxabicyclo[3.2.1]oct-4-ylidene]methyl} benzene-1,2-diamine was used as the ligand in the preparation of the corresponding coordination compounds with palladium(II), copper(II) and nickel(II). The structures were determined by 2D NMR techniques, NOESY spectroscopy and X-ray diffraction. (C) 2004 Elsevier Ltd. All rights reserved.