exo-10,10-diphenyl-10-hydroxymethyl-7,7-dimethylbicyclo[2.2.1]heptane-2-one | 221099-70-3

• 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-10-hydroxymethyl-7,7-dimethylbicyclo[2.2.1]heptane-2-one
• 英文别名: (1R,4R)-7,7-dimethyl-1-(hydroxydiphenylmethyl)-bicyclo[2.2.1]heptan-2-one；10,10-diphenyl-10-hydroxymethyl-7,7-dimethylbicyclo[2.2.1]heptane-2-one；1-(hydroxydiphenylmethyl)-7,7-dimethylbicyclo[2.2.1] heptan-2-one；(1R,4R)-1-(Hydroxydiphenylmethyl)-7,7-dimethylbicyclo[2.2.1]heptan-2-one；(1R,4R)-1-[hydroxy(diphenyl)methyl]-7,7-dimethylbicyclo[2.2.1]heptan-2-one
• CAS: 221099-70-3
• 化学式: C₂₂H₂₄O₂
• 分子量: 320.431
• InChiKey: JDDMEQWGUNGXJH-WIYYLYMNSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.5
• 重原子数：
  24
• 可旋转键数：
  3
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.41
• 拓扑面积：
  37.3
• 氢给体数：
  1
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  exo-10,10-diphenyl-10-hydroxymethyl-7,7-dimethylbicyclo[2.2.1]heptane-2-one 在 lithium aluminium tetrahydride 作用下， 以 四氢呋喃 为溶剂， 反应 0.5h， 以95%的产率得到exo-10,10-diphenyl-2,10-camphanediol
  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：

  (S)-(+)-酮基蒎酸 在 氯化亚砜 、 碘 、 magnesium 作用下， 以 四氢呋喃 为溶剂， 反应 23.0h， 生成 exo-10,10-diphenyl-10-hydroxymethyl-7,7-dimethylbicyclo[2.2.1]heptane-2-one
  参考文献：
  名称：

  通过樟脑衍生物的重排轻松合成异樟脑酸

  摘要：

  通过重排衍生自酮多酸的各种叔醇的樟脑骨架，制备了各种取代的异樟脑酸衍生物。该反应是高度可靠的，并且保留了来自樟脑支架的立体化学信息。这种重排代表了制备合成上有用的异马来酸的有效方法。机理实验表明，该反应涉及短寿命的碳正离子化。

  DOI：

  10.1016/j.tet.2012.12.011

文献信息

• Enantioselective addition of diethylzinc to aldehydes in the presence of chiral hydrazone and imine ligands
  作者：Takashi Mino、Atsushi Suzuki、Masakazu Yamashita、Shusaku Narita、Yoshiaki Shirae、Masami Sakamoto、Tsutomu Fujita

  DOI：10.1016/j.jorganchem.2006.07.006

  日期：2006.10

  Optically active hydrazone and imine were found to act as effective ligands for enantioselective addition of diethylzinc to aldehydes. This reaction provided optically active secondary alcohols with ee up to 71%.

  发现光学活性和亚胺可作为二乙基锌对醛对映选择性加成的有效配体。该反应提供了具有高达71％ee的旋光仲醇。
• Enantioselective Henry reaction catalyzed with copper(II)–iminopyridine complexes
  作者：Gonzalo Blay、Estela Climent、Isabel Fernández、Victor Hernández-Olmos、José R. Pedro

  DOI：10.1016/j.tetasy.2007.06.023

  日期：2007.7

  Copper complexes of chiral iminopyridines prepared from camphane-derived ketones and picolylamine catalyzed the enantioselective Henry (nitroaldol) reaction between nitromethane and a number of aromatic and aliphatic aldehydes with high yields and good enantioselectivities. Iminopyridines derived from (1R)-(+)-camphor and (1S)-(+)-ketopinic acid gave the best results to afford the opposite enantiomers

  由樟脑衍生的酮和甲基吡啶胺制备的手性亚氨基吡啶的铜配合物催化硝基甲烷与许多芳香族和脂肪族醛之间的对映选择性亨利（硝基醛醇）反应，具有高收率和良好的对映选择性。衍生自（1 R）-（+）-樟脑和（1 S）-（+）-酮基酸的亚氨基吡啶在每种情况下均能提供最佳的结果，以提供相反的对映异构体，尽管事实上它们在樟脑中具有相同的立体化学模式骨骼。反应在不排除空气或水分的条件下进行。
• Modular iminopyridine ligands. Application to the enantioselective copper(II)-catalyzed Henry reaction
  作者：Gonzalo Blay、Estela Climent、Isabel Fernández、Victor Hernández-Olmos、José R. Pedro

  DOI：10.1016/j.tetasy.2006.07.025

  日期：2006.8

  Chiral iminopyridines prepared in a modular fashion from monoterpenic (camphor-derived) ketones and pyridinylalkylamines catalyze the enantioselective Henry (nitro aldol) reaction between nitromethane and o-anisol in the presence of copper(II) acetate, with high yields and good ee (up to 86%) under straightforward experimental conditions without the need for air or moisture exclusion.

  由单萜（樟脑油基）酮和吡啶基烷基胺以模块化方式制备的手性亚氨基吡啶，在乙酸铜（II）存在下，催化硝基甲烷和邻苯甲酚之间的对映选择性亨利（硝基羟醛）反应，具有高收率和良好的ee（向上高达86％），而无需排除空气或水分。
• Synthesis of a Camphor-Derived Auxiliary and the Application to the Asymmetric Darzens Reaction
  作者：Yamu Xia、Haixin Liu、Xiaoli Dai

  DOI：10.3184/174751913x13737254410429

  日期：2013.9

  A readily available chiral camphor-derived auxiliary was synthesised through a highly efficient and short general route. The Darzens reaction of the auxiliary with aldehydes in the presence of base gave glycidic esters with almost complete diastereocontrol and high yield.

  通过一条高效、短的通用路线合成了一种现成的手性樟脑衍生助剂。在碱存在下，助剂与醛的 Darzens 反应得到几乎完全非对映控制和高产率的缩水甘油酯。
• Exo-10,10-diphenyl-2,10-camphanediol as a new chiral auxiliary in asymmetric reduction
  作者：Chiou-Juy Chen、Ying-Yuan Chu、Yen-Ying Liao、Zong-Hugh Tsai、Chiung-Chiou Wang、Kwunmin Chen

  DOI：10.1016/s0040-4039(98)02548-9

  日期：1999.2

  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.