6-(benzyloxy)-1,3-cycloheptadiene | 115522-58-2

• 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: 6-(benzyloxy)-1,3-cycloheptadiene
• 英文别名: 6-Phenylmethoxycyclohepta-1,3-diene
• CAS: 115522-58-2
• 化学式: C₁₄H₁₆O
• 分子量: 200.28
• InChiKey: MGDFSHGJFOGDDT-UHFFFAOYSA-N

物化性质

• 沸点：
  297.6±29.0 °C(Predicted)
• 密度：
  1.02±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.6
• 重原子数：
  15
• 可旋转键数：
  3
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.29
• 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：

  6-(benzyloxy)-1,3-cycloheptadiene 在 palladium diacetate 、 palladium on activated charcoal 咪唑 、 sodium hydroxide 、 萘 、 甲烷磺酸 、 四丁基氟化铵 、 氢气 、 sodium 、 potassium carbonate 、 溶剂黄146 、 三乙胺 、 间氯过氧苯甲酸 、 对苯醌 、 lithium chloride 作用下， 以 四氢呋喃 、 甲醇 、 氯仿 、 溶剂黄146 、 二甲基亚砜 、 N,N-二甲基甲酰胺 为溶剂， -78.0~80.0 ℃ 、101.33 kPa 条件下， 反应 200.58h， 生成 pseudoscopine
  参考文献：
  名称：

  Stereocontrolled epoxidations of cycloheptene derivatives in the palladium-catalyzed route to tropane alkaloids. Total syntheses of scopine and pseudoscopine

  摘要：

  Stereoselective total syntheses of the tropane alkaloids scopine (1) and pseudoscopine (3) have been developed via the chloroacetoxylation approach. Palladium-catalyzed 1,4-chloroacetoxylation of diene 6 afforded the key intermediate 7. Subsequent substitution of the allylic chloride by TsNH-with either retention (Pd(O) catalysis) or inversion (S(N)2) of configuration gave 10 and 16, respectively. The epoxy oxygen was introduced syn to the nitrogen function prior to cyclization by utilizing the syn-directive effect of the allylic sulfonamido group in the epoxidation. Cyclization of the epoxides 12 and 21, followed by replacement of the tosyl group by a methyl group and subsequent debenzylation, afforded the title compounds 1 and 3, respectively.

  DOI：

  10.1021/jo00008a037
• 作为产物：
  描述：

  环庚-3,5-二烯-1-醇 、 溴甲苯 在 sodium hydride 作用下， 以 四氢呋喃 为溶剂， 以82%的产率得到6-(benzyloxy)-1,3-cycloheptadiene
  参考文献：
  名称：

  钯催化仲醇的有氧动力学拆分：反应开发、范围和应用

  摘要：

  已经开发出第一个钯催化的仲醇对映选择性氧化反应，利用容易获得的二胺（-）-金雀花石作为手性配体，分子氧作为化学计量氧化剂。关于碱基和氢键供体作用的机制见解导致了对原始系统的一些改进。也就是说，碳酸铯和叔丁醇的添加大大提高了反应速率，促进了快速分辨率。使用氯仿作为溶剂允许在 23 °C 下使用环境空气作为终端氧化剂，从而提高催化剂选择性。这些改进的反应条件使得能够以良好至优异的选择性因子成功地将苄基、烯丙基和环丙基仲醇动力学拆分为高对映体过量。该催化剂体系也已应用于内消旋二醇的去对称化，提供高产率的对映体富集的羟基酮。

  DOI：

  10.1002/chem.200902172

文献信息

• Stereocontrolled synthesis of tropanol derivatives via palladium -catalyzed reactions
  作者：J.E. Bäckvall、Z.D. Renko、S.E. Byström

  DOI：10.1016/s0040-4039(00)95578-3

  日期：——

  A general method for the transformation of 1,3-cycloheptadienes to tropane alkaloid derivatives was developed. The procedure was applied to the stereocontrolled synthesis of the exo- and endo-tropanol derivatives and . The approach is based on a dual stereocontrol in the 1,4-functionalization of conjugated dienes.

  开发了将1，3-环庚二烯转化为托烷生物碱衍生物的通用方法。该方法被用于立体控制合成外，对内醇衍生物和。该方法基于共轭二烯的1,4-官能化中的双重立体控制。
• Stereo- and regioselective palladium-catalyzed 1,4-dialkoxylation of conjugated dienes
  作者：Jan E. Baeckvall、Jan O. Vaagberg

  DOI：10.1021/jo00259a016

  日期：1988.11
• Reagent Control of Geometric Selectivity and Enantiotopic Group Preference in Asymmetric Horner−Wadsworth−Emmons Reactions with <i>meso</i>-Dialdehydes
  作者：Joshua S. Tullis、Lauri Vares、Nina Kann、Per-Ola Norrby、Tobias Rein

  DOI：10.1021/jo981102z

  日期：1998.11.1

  Results from asymmetric Horner-Wadsworth-Emmons reactions between chiral phosphsnate reagents 3a-d, which contain (1R,2S,5R)-8-phenylmenthol as a chiral auxiliary, and meso-dialdehydes 6 and 14 are presented. It was found that both the geometric selectivities and the levels of asymmetric induction depended on the structure of the phosphonate (i.e., the alkyl group R-1 in the phosphoryl unit) and to a certain extent also on the reaction conditions. Furthermore, the nature of the protecting group used on the a-oxygen substituent in dialdehydes 14 influenced the outcome somewhat. By an appropriate choice of reagent and conditions, either (E)- or (Z)-monoaddition products could be obtained geometrically pure and with good to excellent diastereoselectivities, in synthetically useful yields. Analyses of the absolute configurations of the products showed that the (E)-selective reagents (3a-c) and the (Z)-selective phosphonate 3d reacted at opposite enantiotopic carbonyl groups in the substrates. A mechanistic model which accounts for the products formed is presented.
• Asymmetric Horner-Wadsworth-Emmons reactions using meso dialdehydes as substrates
  作者：Nina Kann、Tobias Rein

  DOI：10.1021/jo00067a010

  日期：1993.7

  Asymmetric Horner-Wadsworth-Emmons reactions of the chiral phosphonate 7 with meso dialdehydes 1 and 4 gave the desired monoaddition products with good diastereoselectivities (87:13-97:3) and high (E)-selectivity.
• SCHINK, HANS E.;PETTERSSON, HELENA;BACKVALL, JAN-E., J. ORG. CHEM., 56,(1991) N, C. 2769-2774
  作者：SCHINK, HANS E.、PETTERSSON, HELENA、BACKVALL, JAN-E.

  DOI：——

  日期：——