(1R,2R)-N,N'-bis<(1S,4R)-7,7-dimethyl-2-oxo-bicyclo<2.2.1>heptylmethanesulfonyl>-1,2-cyclohexyldiamine | 167150-88-1

• 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: (1R,2R)-N,N'-bis<(1S,4R)-7,7-dimethyl-2-oxo-bicyclo<2.2.1>heptylmethanesulfonyl>-1,2-cyclohexyldiamine
• 英文别名: trans-(R,R)-N,N'-Bis<(S)-camphersulfonyl>-1,2-cyclohexandiamin；1-[(1S,4R)-7,7-dimethyl-2-oxo-1-bicyclo[2.2.1]heptanyl]-N-[(1R,2R)-2-[[(1S,4R)-7,7-dimethyl-2-oxo-1-bicyclo[2.2.1]heptanyl]methylsulfonylamino]cyclohexyl]methanesulfonamide
• CAS: 167150-88-1
• 化学式: C₂₆H₄₂N₂O₆S₂
• 分子量: 542.761
• InChiKey: XYOKQQGKSGATQM-WLVGUWJVSA-N

物化性质

• 沸点：
  674.2±65.0 °C(Predicted)
• 密度：
  1.31±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.6
• 重原子数：
  36
• 可旋转键数：
  8
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.92
• 拓扑面积：
  143
• 氢给体数：
  2
• 氢受体数：
  8

反应信息

• 作为反应物：
  描述：

  (1R,2R)-N,N'-bis<(1S,4R)-7,7-dimethyl-2-oxo-bicyclo<2.2.1>heptylmethanesulfonyl>-1,2-cyclohexyldiamine 在 sodium tetrahydroborate 作用下， 以 四氢呋喃 、 异丙醇 为溶剂， 以53%的产率得到(1S,2R,4R,1'R,2'R,1''S,2''R,4''R)-N-{trans-2'-[2''-hydroxy-7'',7''-dimethylbicyclo[2.2.1]hept-1''-ylmethylsulfonamino]cyclohexyl}-2-hydroxy-7,7-dimethylbicyclo[2.2.1]hept-1-ylmethanesulfonamide
  参考文献：
  名称：

  A Convenient Method for the Preparation of Inverted tert-Alkyl Carboxylates from Chiral tert-Alcohols by a New Type of Oxidation−Reduction Condensation Using 2,6-Dimethyl-1,4-benzoquinone

  摘要：

  Oxidation-reduction condensation using in situ-formed alkoxydiphenylphosphines, 2,6-dimethyl-1,4-benzoquinone, and carboxylic acids provided a new and efficient method for the preparation of inverted tert-alkyl carboxylates from various chiral tertiary alcohols.

  DOI：

  10.1021/ja0303844
• 作为产物：
  描述：

  右旋樟脑-10-磺酰氯 、 (1R,2R)-1,2-diaminocyclohexane 在 三乙胺 作用下， 以 二氯甲烷 为溶剂， 生成 (1R,2R)-N,N'-bis<(1S,4R)-7,7-dimethyl-2-oxo-bicyclo<2.2.1>heptylmethanesulfonyl>-1,2-cyclohexyldiamine
  参考文献：
  名称：

  烷基与酮的实际催化不对称加成

  摘要：

  许多催化剂会促进烷基锌试剂与醛的不对称加成。相比之下，没有关于添加通用和高度对映选择性的酮的报告。我们在本文中描述了乙基与酮的实际催化不对称加成。该催化剂来源于樟脑磺酰氯与反式-1,2-二氨基环己烷的反应。得到的二酮用 NaBH4 还原，得到 C2 对称的外型非对映异构体。在室温下将该配体与四异丙醇钛和二烷基锌一起使用导致烷基与酮的对映选择性加成。得到的叔醇以高对映体过量进行分离（所有情况都产生大于 87% 的 ee，除了一种）。

  DOI：

  10.1021/ja026568k
• 作为试剂：
  描述：

  Dimethylzinc 、 苯丙酮 在 titanium(IV) isopropylate 、 (1R,2R)-N,N'-bis<(1S,4R)-7,7-dimethyl-2-oxo-bicyclo<2.2.1>heptylmethanesulfonyl>-1,2-cyclohexyldiamine 作用下， 以 甲苯 为溶剂， 反应 8.0h， 以95%的产率得到(R)-2-phenyl-butan-2-ol
  参考文献：
  名称：

  Highly enantioselective addition of dialkylzinc reagents to ketones promoted by titanium tetraisopropoxide

  摘要：

  The preparation of several 1,2-bis(hydroxycamphorsulfonamido)cyclo exenes from the corresponding 1,2-cyclohexenediamine and camphorsulfonyl chloride is described. The use of these ligands to promote the enantio selective addition of dialkylzinc to ketones in the presence of titanium tetraisopropoxide gives the expected tertiary alcohols with very high enantiomeric excess (>99%). (C) 2002 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0957-4166(02)00572-4

文献信息

• Synthesis of camphorsulfonamide-based quinoline ligands and their N-oxides: first use in the enantioselective addition of organozinc reagents to aldehydes
  作者：Ricardo Martínez、Luca Zoli、Pier Giorgio Cozzi、Diego J. Ramón、Miguel Yus

  DOI：10.1016/j.tetasy.2008.10.020

  日期：2008.11

  The preparation of several camphorsulfonamide-based quinoline derivatives and their N-oxides was accomplished via an indirect Friedländer synthesis using aminobenzylic alcohols and RuCl2(DMSO)4 as a catalyst. These ligands were tested in the enantioselective addition of dialkylzinc reagents to aldehydes, with enantiomeric excesses up to 96%. A similar protocol using triphenylborane and diethylzinc

  几种基于樟脑磺酰胺的喹啉衍生物及其N-氧化物的制备，是通过使用氨基苄醇和RuCl 2（DMSO）4作为催化剂的间接Friedländer合成完成的。在二烷基锌试剂对醛的对映选择性加成中，对这些配体进行了测试，对映体过量最高达96％。使用三苯基硼烷和二乙基锌的类似方案给出了相应的苯化过程。
• A Practical Catalytic Asymmetric Addition of Alkyl Groups to Ketones
  作者：Celina García、Lynne K. LaRochelle、Patrick J. Walsh

  DOI：10.1021/ja026568k

  日期：2002.9.1

  Many catalysts will promote the asymmetric addition of alkylzinc reagents to aldehydes. In contrast, there are no reports of additions to ketones that are both general and highly enantioselective. We describe herein a practical catalytic asymmetric addition of ethyl groups to ketones. The catalyst is derived from reaction of camphor sulfonyl chloride and trans-1,2-diaminocyclohexane. The resulting

  许多催化剂会促进烷基锌试剂与醛的不对称加成。相比之下，没有关于添加通用和高度对映选择性的酮的报告。我们在本文中描述了乙基与酮的实际催化不对称加成。该催化剂来源于樟脑磺酰氯与反式-1,2-二氨基环己烷的反应。得到的二酮用 NaBH4 还原，得到 C2 对称的外型非对映异构体。在室温下将该配体与四异丙醇钛和二烷基锌一起使用导致烷基与酮的对映选择性加成。得到的叔醇以高对映体过量进行分离（所有情况都产生大于 87% 的 ee，除了一种）。
• trans-1-Sulfonylamino-2-isoborneolsulfonylaminocyclohexane Derivatives: Excellent Chiral Ligands for the Catalytic Enantioselective Addition of Organozinc Reagents to Ketones
  作者：Vicente J. Forrat、Oscar Prieto、Diego J. Ramón、Miguel Yus

  DOI：10.1002/chem.200501397

  日期：2006.5.24

  The catalytic enantioselective addition of different organozinc reagents (such as alkyl and aryl derivatives or in situ generated aryl, allyl alkenyl, and alkynyl derivatives obtained through different transmetallation processes) to simple ketones has been accomplished by using titanium tetraisopropoxide and chiral ligands derived from substituted trans-1-sulfonylamino-2-isoborneolsulfonylaminocyclohexane

  通过使用四异丙氧基钛和衍生自取代的反式-1-磺酰基氨基-2-异冰片醇磺酰基氨基环己烷，生成相应的叔醇，对映体过量（ee）最高> 99％。描述了一种简单有效的合成这些反应中使用的手性配体的方法。
• Gerlach, Uwe; Haubenreich, Thomas; Huenig, Siegfried, Chemische Berichte, 1994, vol. 127, # 10, p. 1969 - 1980
  作者：Gerlach, Uwe、Haubenreich, Thomas、Huenig, Siegfried

  DOI：——

  日期：——
• Enantioselective addition of diethylzinc to aldehydes induced by a new chiral Ti(IV) catalyst
  作者：Chyuan-Der Hwang、Biing-Jiun Uang

  DOI：10.1016/s0957-4166(98)00415-7

  日期：1998.11

  A new chiral titanium reagent, derived from optically active trans-1,2-dicamphorsulfonamidocyclohexane 2a and Ti((OPr)-Pr-i)(4), was found to promote the enantioselective addition of diethylzinc to various aldehydes giving rise to the corresponding alcohols in high yields with moderate to high selectivity. (C) 1998 Published by Elsevier Science Ltd. All rights reserved.