exo-10,10-diphenyl-2,10-camphanediol | 221099-71-4

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: exo-10,10-diphenyl-2,10-camphanediol
• 英文别名: (1S,2R,4R)-1-[hydroxy(diphenyl)methyl]-7,7-dimethylbicyclo[2.2.1]heptan-2-ol
• CAS: 221099-71-4
• 化学式: C₂₂H₂₆O₂
• 分子量: 322.447
• InChiKey: TWVCCLVOHQSTGB-SFHLNBCPSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.9
• 重原子数：
  24
• 可旋转键数：
  3
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.45
• 拓扑面积：
  40.5
• 氢给体数：
  2
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  exo-10,10-diphenyl-2,10-camphanediol 在 18-冠醚-6 、 potassium tri-sec-butyl-borohydride 、 三乙胺 作用下， 以 二氯甲烷 为溶剂， 反应 0.5h， 生成 [(1S,2R,4R)-1-[hydroxy(diphenyl)methyl]-7,7-dimethyl-2-bicyclo[2.2.1]heptanyl] (2S)-2-hydroxypropanoate
  参考文献：
  名称：

  Novel Camphor-Derived Chiral Auxiliaries:  Significant Solvent and Additive Effects on Asymmetric Reduction of Chiral α-Keto Esters

  摘要：

  Stereoselective reduction of various alpha-keto esters 5a-d derived from exo-10,10-diphenyl-2,10-camphanediol 4a and exo-10,10-diphenyl-10-methoxy-2-camphanol 4b is described. High to excellent diastereomeric excess (99% de) with good chemical yields is obtained. The sense of stereoselectivity as a function of C10 modification is remarkable. Further, in the case of 5d, both diastereomers of a-hydroxyl esters can be obtained with excellent optical purity by the appropriate choice of reaction conditions. The influence of the solvents and additives on the reaction course has been investigated.

  DOI：

  10.1021/jo9902188
• 作为产物：
  描述：

  [(1S,2R,4R)-1-[hydroxy(diphenyl)methyl]-7,7-dimethyl-2-bicyclo[2.2.1]heptanyl] 2-oxo-2-phenylacetate 在 sodium hydroxide 、 LiAlH(OCEt₃)3 、 水 作用下， 以 四氢呋喃 为溶剂， 反应 0.17h， 生成 exo-10,10-diphenyl-2,10-camphanediol
  参考文献：
  名称：

  Exo-10,10-diphenyl-2,10-camphanediol as a new chiral auxiliary in asymmetric reduction

  摘要：

  Stereoselective reduction of alpha-keto ester derived from exo-10, 10-diphenyl-2, 10-camphanediol with various hydrides proceeded with high diastereoselectivities (greater than or equal to 96% de) to afford the corresponding alpha-hydroxy ester with excellent yields. Change of reducing reagents and molar ratio modifications leading to dramatic changes in diastereofacial selectivity were examined. The auxiliary can be recovered from the asymmetric reaction products without loss of chirality. (C) 1999 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0040-4039(98)02548-9

文献信息

• anti-Aldol reactions of chiral alcohol-substituted vinylogous urethanes and the synthesis of (−)-prelactone B
  作者：Yu-Jang Li、Hsiu-Yin Hung、Yu-Wei Liu、Pei-Jhen Lin、Hung-Jyun Huang

  DOI：10.1016/j.tet.2010.12.009

  日期：2011.2

  alcohol-substituted vinylogous urethanes, in which the double bond has E configuration was determined by single crystal X-ray analysis. In addition, we investigated the anti-aldol reactions of these chiral vinylogous urethane anions. The use of (1S,2R,4R)-1-(hydroxydiphenylmethyl)-7,7-dimethylbicyclo[2,2,1]-heptan-2-ol as a chiral auxiliary, provided the best enantioselectivities, and the resulting vinylogous urethane

  本文描述了一种方便有效的合成手性醇取代的乙烯基氨基甲酸酯的方法，其中通过单晶X射线分析确定了具有E构型的双键。另外，我们研究了这些手性乙烯基类氨基甲酸酯阴离子的抗醛醇缩合反应。使用（1 S，2 R，4 R）-1-（羟基二苯甲基）-7,7-二甲基双环[2,2,1]-庚-2-醇作为手性助剂，可提供最佳对映选择性，并且所得的乙烯基类氨基甲酸酯内酯可用于合成（-）-内酯B。讨论了主要对映异构体生成的合理机理。
• 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。
• anti-Selective aldol reactions of chiral alcohol substituted γ-benzyloxyl vinylogous urethanes and the synthesis of 3-benzyloxyl-4-hydroxylalkan-2-ones
  作者：Yu-Jang Li、Chuan-Chung Chung、Pin-Zu Chen

  DOI：10.1016/j.tetasy.2017.10.003

  日期：2017.11

  The anti-selective aldol reaction of chiral alcohol-substituted gamma-benzyloxy vinylogous urethanes is described. The use of (1S,2R,4R)-1-(hydroxydiphenylmethyl)-7,7-dimethylbicyclo[2,2,1]-heptan-2-ol as a chiral auxiliary in the aldol reaction of a vinylogous urethane enolate was found to provide anti-products in good yields with moderate to excellent enantioselectivities. The major anti-vinylogous urethane lactones were transformed into 3-benzyloxyl-4-hydroxylalkan-2-ones in good yields. (C) 2017 Elsevier Ltd. All rights reserved.
• On the scope of diastereoselective aziridination of various chiral auxiliaries derived N- and O-enones with N-aminophthalimide in the presence of lead tetraacetate
  作者：Pei-Wen Duan、Ching-Chen Chiu、Wei-Der Lee、Li Shiue Pan、Uppala Venkatesham、Zheng-Hao Tzeng、Kwunmin Chen

  DOI：10.1016/j.tetasy.2008.02.028

  日期：2008.4

  The treatment of a range of N- and O-enones derived from various camphor-based chiral auxiliaries A-D with N-aminoplithalimide in the presence of lead tetraacetate is described. In general, N-phtbalimidoaziridines were obtained with high diastereo-selectivities (up to 98% de) and chemical yields (up to 95%) when 10,10-diphenyl-2,10-camphanediol A derived O-enones with a range of substituents were used under the same reaction conditions. Excellent stereoselectivity was obtained when the N-tosyl camphorpyrazolidinone E derived acrylate was used. The absolute configuration of the new stereogenic center(s) of the major diastereomer was established by X-ray crystallographic analysis. Chiral auxiliary cleavage was achieved under mild reaction conditions. A model to explain the stereochemical induction is also proposed. (c) 2008 Elsevier Ltd. All rights reserved.
• Asymmetric [2,3]-Wittig rearrangement of the dienolates of chiral secondary alcohol-substituted β-pyrrolidinyl-γ-allyloxyl-α,β-unsaturated esters: total synthesis of (+)-eldanolide
  作者：Yu-Jang Li、Guo-Ming Ho、Pin-Zu Chen

  DOI：10.1016/j.tetasy.2009.07.028

  日期：2009.8

  The asymmetric [2,3]-Wittig rearrangement of the dienolates of various chiral beta-pyrrolidinyl-gamma-allyloxyl-alpha,beta-unsaturated esters was investigated using different chiral secondary alcohol Substitutions. When (1S,2R,4R)-2-hydroxy-7,7-dimethylbicyclo[2,2,1]heptane-1-carboxylic acid diisopropylamide was used as chiral auxiliary, it provided the best enantioselectivity in the rearrangement. When various gamma-allyloxy substitutions underwent temperature and additive studies, 1,1-dimethylpropenoxy substitution was found to give the best enantioselectivity. The methodology was applied to the total synthesis of eldanolide. (C) 2009 Elsevier Ltd. All rights reserved.