(1R,2S)-trans-2-phenyl-1-(1(E)-propenyloxy)cyclohexane | 147253-76-7

• 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: (1R,2S)-trans-2-phenyl-1-(1(E)-propenyloxy)cyclohexane
• 英文别名: [(1S,2R)-2-[(E)-prop-1-enoxy]cyclohexyl]benzene
• CAS: 147253-76-7
• 化学式: C₁₅H₂₀O
• 分子量: 216.323
• InChiKey: IORVFUZSVMLBHS-JBFDKDDQSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.3
• 重原子数：
  16
• 可旋转键数：
  3
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.47
• 拓扑面积：
  9.2
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  (2E,6E)-methyl 7-nitro-2,6-octadienoate 、 (1R,2S)-trans-2-phenyl-1-(1(E)-propenyloxy)cyclohexane 在 Ti(OiPr)Cl3 作用下， 生成 octahydro-5,7b-dimethyl-6-<(1R,2S)-2-(phenylcyclohexyl)oxy>-1,7-dioxa-7a-azacyclopentindene-2-carboxylic acid methyl ester
  参考文献：
  名称：

  Tandem Cycloaddition Chemistry of Nitroalkenes:  Probing the Remarkable Stereochemical Influence of the Lewis Acid

  摘要：

  The influence of several Lewis acids on the stereochemical course of the [4 + 2] cycloaddition of nitroalkene 1 and chiral, nonracemic propenyl ether 8 has been examined. All of the Lewis acids examined favored ul relative diastereoselection ("exo" approach); TiCl4, TiBr3(Oi-Pr), SnCl4, and ATPh were the most selective. Within the titanium-based Lewis acids, it was found that increasing the halide-to-alkoxide ratio increased the degree of ul (relative) selectivity, as did switching from chloride to bromide. The internal diastereoselectivity was also dependent on the Lewis acid; most titanium isopropoxide-halides (bromide and chloride) and SnCl4 were highly selective for (1,3-lk) approach, with the selectivity increasing with increasing halide content. Two aluminum-based Lewis acids (MAPh and ATPh) were selective for the opposite-sense of internal diastereoselection. The high Ik (relative) diastereoselectivity observed only with TiCl2(Oi-Pr)(2) is proposed to arise either from Coulombic stabilization of an endo approach or precomplexation of the vinyl ether to the Lewis acid. The switch in internal diastereoselectivity seen in the exo manifold is thought to arise from subtle changes in the steric nature of the Lewis acid-nitroalkene complex.

  DOI：

  10.1021/jo9820869
• 作为产物：
  描述：

  (1R,2S)-trans-2-phenyl-1-(1-propynyloxy)cyclohexane 在 红铝 作用下， 以 四氢呋喃 为溶剂， 反应 4.0h， 以83%的产率得到(1R,2S)-trans-2-phenyl-1-(1(E)-propenyloxy)cyclohexane
  参考文献：
  名称：

  （E）和（Z）O-烷基烯醇醚的不同立体选择性合成

  摘要：

  虽然用氢化铝锂（或用双（2-甲氧基乙氧基）氢化铝钠还原炔基醚）几乎只得到具有（E）构型的O-烷基烯醇醚，但用双（2-甲氧基乙氧基）氢化铝钠进行了反应预处理与一当量的游离醇形成的立体异构地导致具有（Z）构型的烯醇醚。

  DOI：

  10.1016/s0040-4039(00)78881-2

文献信息

• Enantioselective [4 + 2] Cycloadditions of <i>o</i>-Quinone Methides:  Total Synthesis of (+)-Mimosifoliol and Formal Synthesis of (+)-Tolterodine
  作者：Carolyn Selenski、Thomas R. R. Pettus

  DOI：10.1021/jo048703c

  日期：2004.12.1

  The first example of an enantioselective cycloaddition of an o-quinone methide (o-QM) with a chiral enol ether is described along with the total synthesis of (+)-mimosifoliol and the formal synthesis of (+)-tolterodine. These syntheses exemplify a three-component, one-pot benzopyran approach for the construction of chiral benzylic junctions. Cycloadditions of various enol ethers and o-QMs are examined

  描述了邻醌甲基化物（o- QM）与手性烯醇醚的对映选择性环加成的第一个实例，以及（+）-米莫西福尔的全合成和（+）-托特罗定的形式合成。这些合成例证了用于手性苄基连接的三组分一锅苯并吡喃方法。研究了各种烯醇醚和邻-QM的环加成反应，用反式-2-苯基-1-环己醇和2,2-二苯基环戊醇乙烯基醚得到的非对映选择性> 95％。
• Divergent stereoselective synthesis of (E) and (Z) O-Alkyl enol ethers
  作者：Lluís Solá、Jaume Castro、Albert Moyano、Miquel A. Pericás、Antoni Riera

  DOI：10.1016/s0040-4039(00)78881-2

  日期：1992.5

  While the reduction of alkynyl ethers with lithium aluminum hydride (or with sodium bis(2-methoxyethoxy) aluminum hydride) gives almost exclusively O-alkyl enol ethers with (E) configuration, the reaction with sodium bis(2-methoxyethoxy) aluminum hydride pretreated with one equivalent of a free alcohol leads stereoselectively to enol ethers with (Z) configuration.

  虽然用氢化铝锂（或用双（2-甲氧基乙氧基）氢化铝钠还原炔基醚）几乎只得到具有（E）构型的O-烷基烯醇醚，但用双（2-甲氧基乙氧基）氢化铝钠进行了反应预处理与一当量的游离醇形成的立体异构地导致具有（Z）构型的烯醇醚。
• Tandem inter [4+2]/intra [3+2]nitroalkene cycloadditions. 5. Origin of the Lewis acid dependent reversal of stereoselectivity
  作者：Scott E. Denmark、Mark E. Schnute、C. B. W. Senanayake

  DOI：10.1021/jo00059a044

  日期：1993.3

  The stereochemical course of the tandem [4 + 2]/[3 + 2] nitroalkene cycloaddition with chiral enol ethers has been shown to exhibit remarkable sensitivity to the nature of the Lewis acid promoter. Cycloadditions using (+)-camphor-derived vinyl ether 3 or (-)-trans-2-phenylcyclohexanol-derived vinyl ether 6 gave a predominance of the 1S hydroxy lactam 4 when promoted by Ti(O-i-Pr)2Cl2. The same vinyl ethers selectively produced the 1R hydroxy lactam 4 when promoted by MAPh. The (E)- and (Z)-1-propenyl ethers of (-)-trans-2-phenylcyclohexanol have been used to investigate the reversal of selectivity. Cycloadditions promoted by Ti(O-i-Pr)2Cl2 were found to be endo selective (12:1), while MAD and MAPh favored exo approach of the dienophile. High levels of asymmetric induction were observed in the endo mode of the cycloaddition for propenyl ethers (E)-13 and (Z)-13, 97.9% ee and 82.2% ee, respectively, but an erosion of selectivity occurred in the exo mode (72.2% ee) presumably through an s-cis enol ether conformation.
• Tandem Cycloaddition Chemistry of Nitroalkenes:  Probing the Remarkable Stereochemical Influence of the Lewis Acid
  作者：Scott E. Denmark、Mark Seierstad

  DOI：10.1021/jo9820869

  日期：1999.3.1

  The influence of several Lewis acids on the stereochemical course of the [4 + 2] cycloaddition of nitroalkene 1 and chiral, nonracemic propenyl ether 8 has been examined. All of the Lewis acids examined favored ul relative diastereoselection ("exo" approach); TiCl4, TiBr3(Oi-Pr), SnCl4, and ATPh were the most selective. Within the titanium-based Lewis acids, it was found that increasing the halide-to-alkoxide ratio increased the degree of ul (relative) selectivity, as did switching from chloride to bromide. The internal diastereoselectivity was also dependent on the Lewis acid; most titanium isopropoxide-halides (bromide and chloride) and SnCl4 were highly selective for (1,3-lk) approach, with the selectivity increasing with increasing halide content. Two aluminum-based Lewis acids (MAPh and ATPh) were selective for the opposite-sense of internal diastereoselection. The high Ik (relative) diastereoselectivity observed only with TiCl2(Oi-Pr)(2) is proposed to arise either from Coulombic stabilization of an endo approach or precomplexation of the vinyl ether to the Lewis acid. The switch in internal diastereoselectivity seen in the exo manifold is thought to arise from subtle changes in the steric nature of the Lewis acid-nitroalkene complex.