7,7-dimethyl-2'-phenyl-pyrazol-3'-one-bicyclo[2.2.1]heptane | 263722-72-1

• 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-2'-phenyl-pyrazol-3'-one-bicyclo[2.2.1]heptane
• 英文别名: N²-phenyl camphorpyrazolidinone；(+)-(2R)-bornane-10,2-cyclohydrazide；(1S,5R,7R)-10,10-dimethyl-3-phenyl-3,4-diazatricyclo[5.2.1.01,5]decan-2-one
• CAS: 263722-72-1
• 化学式: C₁₆H₂₀N₂O
• 分子量: 256.348
• InChiKey: QWLWHNMMQFVFFO-KFNAQCHYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.9
• 重原子数：
  19
• 可旋转键数：
  1
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.56
• 拓扑面积：
  32.3
• 氢给体数：
  1
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  7,7-dimethyl-2'-phenyl-pyrazol-3'-one-bicyclo[2.2.1]heptane 在 三乙烯二胺 、 三乙胺 作用下， 以 二氯甲烷 、 二甲基亚砜 为溶剂， 反应 96.5h， 生成
  参考文献：
  名称：

  Diastereoselective Baylis−Hillman Reactions:  The Design and Synthesis of a Novel Camphor-Based Chiral Auxiliary

  摘要：

  Reaction of chiral acryloylhydrazide 5 derived from novel auxiliary 4 with aldehydes in the presence of DABCO affords practical levels (up to 98% de) of beta-hydroxy-alpha-methylene carbonyl derivatives, and high optical purity of both diastereomers of 6a-d and 7a-d can be obtained by changing the solvent.

  DOI：

  10.1021/ol990315n
• 作为产物：
  描述：

  (S)-(+)-酮基蒎酸 在 sodium tetrahydroborate 、 氯化亚砜 、 溶剂黄146 、 三乙胺 作用下， 以 甲醇 、 二氯甲烷 、 乙酸乙酯 为溶剂， 反应 11.0h， 生成 7,7-dimethyl-2'-phenyl-pyrazol-3'-one-bicyclo[2.2.1]heptane
  参考文献：
  名称：

  Diastereoselective Baylis−Hillman Reactions:  The Design and Synthesis of a Novel Camphor-Based Chiral Auxiliary

  摘要：

  Reaction of chiral acryloylhydrazide 5 derived from novel auxiliary 4 with aldehydes in the presence of DABCO affords practical levels (up to 98% de) of beta-hydroxy-alpha-methylene carbonyl derivatives, and high optical purity of both diastereomers of 6a-d and 7a-d can be obtained by changing the solvent.

  DOI：

  10.1021/ol990315n

文献信息

• A comparison of two effective chiral auxiliaries—(2R)-bornane-10,2-sultam and (2R)-bornane-10,2-cyclohydrazide—using the [4+2] cycloaddition of cyclopentadiene to their N,N′-fumaroyl derivatives
  作者：Christian Chapuis、Anna Kucharska、Janusz Jurczak*

  DOI：10.1016/s0957-4166(00)00436-5

  日期：2000.11

  uncatalyzed [4+2] cycloaddition of cyclopentadiene to N,N′-fumaroyldi[(2R)-bornane-10,2-(2′-phenyl-pyrazol-3′-one)]. Using the Abboud–Abraham–Kamlet–Taft parameters, predictive values for this method resulted in an optimum diastereoisomeric excess (de) of more than 97% in hexane. Implications for the stereochemical course of the reaction as well as a comparison with the analogous (2R)-bornane-10,2-sultam auxiliary

  发现环戊二烯未催化的[4 + 2]环加成反应成N，N'-富马酰基二[（2 R）-冰片烷10,2-（2）时，溶剂极性与非对映异构体比率（dr）的对数之间存在相关性。'-苯基-吡唑-3'-one）]。使用Abboud–Abraham–Kamlet–Taft参数，此方法的预测值可导致己烷中非对映异构体的最佳过量（de）超过97％。讨论了对反应的立体化学过程的暗示以及与类似的（2 R）-冰片烷10,2-磺胺助剂的比较。
• Diastereoselective [3+2] cycloadditions of a camphor-derived chiral N-acryloylhydrazide with nitrile oxides: the preparation of optically pure Δ2-isoxazolines
  作者：Kung-Shuo Yang、Jung-Chaing Lain、Chun-Hui Lin、Kwunmin Chen

  DOI：10.1016/s0040-4039(99)02316-3

  日期：2000.2

  Reaction of a novel chiral N-acryloylhydrazide with various nitrile oxides proceeded smoothly to afford the cycloadduct with high diastereoselectivity (99:1). The auxiliary can be easily removed from the cycloadducts under mild conditions.

  新型手性N-丙烯酰肼与各种腈氧化物的反应进行得很顺利，从而得到具有高非对映选择性（99：1）的环加合物。在温和的条件下，可以轻松地从环加合物中除去辅助剂。
• On the scope of diastereoselective allylation of various chiral glyoxylic oxime ethers with allyltributylstannane in the presence of a Lewis acid and triallylaluminum
  作者：Neelesh A. Kulkarni、Ching-Fa Yao、Kwunmin Chen

  DOI：10.1016/j.tet.2007.05.091

  日期：2007.8

  The nucleophilic allylation of various chiral auxiliaries derived glyoxylic oxime ethers was studied. The use of allyltributylstannane in the presence of a Lewis acid and triallylaluminum provided the corresponding homoallylic amines in high chemical yields (up to 89%) and excellent stereoselectivities (up to >99%). The stereochemical bias of the allylation is proposed.

  研究了各种手性助剂衍生的乙醛酸肟醚的亲核烯丙基化。在路易斯酸和三烯丙基铝存在下使用烯丙基三丁基锡烷以高化学产率（高达89％）和出色的立体选择性（高达> 99％）提供了相应的均烯丙基胺。提出了烯丙基化的立体化学偏倚。
• An Efficient and Convenient Synthesis of Ethyl 1-(4-Methoxyphenyl)-5-phenyl-1<i>H</i>-1,2,3-triazole-4-carboxylate
  作者：Jung-Hsuan Chen、Shuan-Ru Liu、Kwunmin Chen

  DOI：10.1002/asia.200900320

  日期：2010.2.1

  The “click chemistry” of using organic azides and terminal alkynes is arguably the most efficient and straightforward route to the synthesis of 1,2,3‐triazoles. In this paper, an alternative and direct access to ethyl 1‐(4‐methoxyphenyl)‐5‐phenyl‐1H‐1,2,3‐triazole‐4‐carboxylate is described. Treatment of ethyl diazoacetate with 4‐methoxyaniline derived aryl imines in the presence of 1,8‐diazabicyclo[5

  使用有机叠氮化物和末端炔烃的“点击化学”可以说是合成1,2,3-三唑的最有效，最直接的途径。本文提供了一种直接替代乙基1-（4-甲氧基苯基）-5-苯基-1 H的方法描述了1,2,3-三唑-4-羧酸酯。在1,8-二氮杂双环[5.4.0]十一碳-7-烯存在下，用4-甲氧基苯胺衍生的芳基亚胺处理重氮乙酸乙酯可提供完全取代的1,2,3-三唑，化学产率高至高。碱介导的反应耐受各种取代的苯基亚胺以及重氮乙酸乙酯或更大体积的重氮乙酰胺。提出了一种合理的机理，其中包括在重氮化合物的末端氮原子上添加一个亚胺氮原子，然后进行芳构化以生成1,2,3-三唑。4-羧基的存在是有利的，因为它可以很容易地转化成其他官能团。
• Diastereoselective electrophilic α-amination of camphor N1-acyl N2-phenylpyrazolidinones: the metal enolate-dependent synthesis of two possible hydrazide diastereomers
  作者：Chin-Sheng Chao、Chung-Kai Cheng、Ssu-Hsien Li、Kwunmin Chen

  DOI：10.1016/j.tetlet.2008.11.003

  日期：2009.1

  Complementary approaches under enolate amination reactions for the synthesis of both α-hydrazidoacyl diastereomers have been achieved. Both isomers are obtained with high to excellent chemical yields and high stereoselectivities (up to >95:5 dr) when aryl-substituted camphor N1-acyl N2-phenylpyrazolidinone was treated with potassium hexamethyldisilylamide (KHMDS) and lithium hexamethyldisilylamide

  已经实现了在烯醇化胺反应下用于合成两种α-肼基酰基非对映异构体的补充方法。使用六甲基二甲硅烷基氨基钾（KHMDS）和六甲基二甲硅烷基锂（LHMDS）处理芳基取代的樟脑N 1-酰基N 2-苯基吡唑烷二酮时，两种异构体均具有很高的化学产率和很高的立体选择性（高达> 95：5 dr ），分别加入偶氮二羧酸二叔丁酯。可以在温和条件下进行的无损手性助剂的除去，提供了具有高对映体比率的酰肼醇。讨论了反应的面部立体选择性和立体化学过程。