(4R,6R)-(-)-5,5-dimethyl-4,6-methano-(N-methylacetamido)-cyclohexene | 304857-37-2

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羧酸及其衍生物
• 英文名称: (4R,6R)-(-)-5,5-dimethyl-4,6-methano-(N-methylacetamido)-cyclohexene
• 英文别名: N-[(1R,5S)-6,6-dimethyl-2-bicyclo[3.1.1]hept-2-enyl]acetamide
• CAS: 304857-37-2
• 化学式: C₁₁H₁₇NO
• 分子量: 179.262
• InChiKey: AQOOXVCCLFKKBB-IUCAKERBSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.6
• 重原子数：
  13
• 可旋转键数：
  1
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.73
• 拓扑面积：
  29.1
• 氢给体数：
  1
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  (4R,6R)-(-)-5,5-dimethyl-4,6-methano-(N-methylacetamido)-cyclohexene 在 三苯基膦 、 nickel dichloride 、 锌 、 三氯氧磷 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 反应 25.0h， 生成 (6R,6R',8R,8R')-(+)-5,5',6,6',7,7',8,8'-octahydro-7,7,7',7'-tetramethylbi(6,8-methanoquinoline)
  参考文献：
  名称：

  PINDY:  A Novel, Pinene-Derived Bipyridine Ligand and Its Application in Asymmetric, Copper(I)-Catalyzed Allylic Oxidation

  摘要：

  [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).

  DOI：

  10.1021/ol006111k
• 作为产物：
  描述：

  beta-pinene 在 吡啶 、 sodium periodate 、 四氧化锇 、 十二/十四烷基二甲基氧化胺 、 盐酸羟胺 、 铁粉 、 溶剂黄146 作用下， 以 乙醇 、 水 、 甲苯 、 叔丁醇 为溶剂， 反应 2.17h， 生成 (4R,6R)-(-)-5,5-dimethyl-4,6-methano-(N-methylacetamido)-cyclohexene
  参考文献：
  名称：

  PINDY:  A Novel, Pinene-Derived Bipyridine Ligand and Its Application in Asymmetric, Copper(I)-Catalyzed Allylic Oxidation

  摘要：

  [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).

  DOI：

  10.1021/ol006111k

文献信息

• Catalyst-free and oxidant-free tandem aza-Mannich/cyclization/aromatization of <i>C</i>,<i>N</i>-cyclic azomethine imines with enamides: facile synthesis of 5,6-dihydropyrazolo[5,1-<i>a</i>]isoquinolines
  作者：Hao Dong、Yongxing Zhang、Xiaochen Tian、Ruochen Pang、Weiwu Ren、Yang Wang

  DOI：10.1039/d2gc01275h

  日期：——

  tandem aza-Mannich/cyclization/aromatization reaction of C,N-cyclic azomethine imines with enamides has been developed. This practical one-step protocol enables a simple and environmentally friendly route toward the straightforward synthesis of highly substituted 5,6-dihydropyrazolo[5,1-a]isoquinolines. Different types of enamides and enamines, especially enamides derived from marketed drugs as well as bioactive

  开发了一种新型高效的无催化剂、无氧化剂串联氮杂曼尼希/环化/芳构化C , N-环偶氮甲亚胺与烯酰胺反应。这种实用的一步法为直接合成高度取代的 5,6-二氢吡唑并[5,1- a ] 异喹啉提供了一种简单且环保的途径。不同类型的烯酰胺和烯胺，尤其是衍生自上市药物以及生物活性分子的烯酰胺，是合适的底物。CB1 大麻素受体拮抗剂可以基于该方法有效合成，说明这将是合成有价值的结构基序的实用策略。
• New Lewis-Basic <i>N</i>-Oxides as Chiral Organocatalysts in Asymmetric Allylation of Aldehydes
  作者：Andrei V. Malkov、Mark Bell、Monica Orsini、Daniele Pernazza、Antonio Massa、Pavel Herrmann、Premji Meghani、Pavel Kočovský

  DOI：10.1021/jo035074i

  日期：2003.12.1

  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.