1-[(tert-butyldimethylsiloxy)methyl]-1,4-epoxy-1,4-dihydronaphthalene

• 分子结构分类: 有机化合物 - 苯类化合物 - 萘
• 英文名称: 1-[(tert-butyldimethylsiloxy)methyl]-1,4-epoxy-1,4-dihydronaphthalene
• 英文别名: 1-((tert-butyldimethylsilyloxy)methyl)oxabenzonorbornene；tert-butyl-dimethyl-[[(1R,8S)-11-oxatricyclo[6.2.1.02,7]undeca-2,4,6,9-tetraen-1-yl]methoxy]silane
• 化学式: C₁₇H₂₄O₂Si
• 分子量: 288.462
• InChiKey: KMIQGOYLVRUOFL-RDJZCZTQSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.54
• 重原子数：
  20
• 可旋转键数：
  4
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.53
• 拓扑面积：
  18.5
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  1-[(tert-butyldimethylsiloxy)methyl]-1,4-epoxy-1,4-dihydronaphthalene 在 四氧化锇 、 水 、 N-甲基吗啉氧化物 作用下， 以 丙酮 为溶剂， 以92.1 mg的产率得到(1R,2R,3S,4R)-1-((tert-butyldimethylsilyloxy)methyl)-2,3-dihydroxy-1,4-epoxy-1,2,3,4-tetrahydronaphthalene
  参考文献：
  名称：

  Conformational Effects in Diastereoselective Aryne Diels−Alder Reactions: Synthesis of Benzo-Fused [2.2.1] Heterobicycles

  摘要：

  It was found that the diastereoselectivity of the Diels-Alder reaction between arynes and substituted furans is highly sensitive to substitution, which affects the reactive conformation. By varying the location of the groups on the diene partner, it is possible to obtain both excellent chemical yields and high stereoselectivity. This methodology offers rapid and convenient access to enantiomerically pure bicyclic scaffolds which are difficult to prepare by other means.

  DOI：

  10.1021/ol9019869
• 作为产物：
  描述：

  [(1R,8S)-11-oxatricyclo[6.2.1.02,7]undeca-2,4,6,9-tetraen-1-yl]methanol 、 叔丁基二甲基氯硅烷 在 咪唑 作用下， 以 二氯甲烷 为溶剂， 反应 16.0h， 以83%的产率得到1-[(tert-butyldimethylsiloxy)methyl]-1,4-epoxy-1,4-dihydronaphthalene
  参考文献：
  名称：

  使用阳离子铑催化剂的不对称氧杂双环烯烃的试剂控制区域发散拆分

  摘要：

  Rh(I) 催化的杂原子亲核试剂向外消旋氧杂双环烯烃的区域发散加成产生了高 ee 的区域异构产物的良好产率。证明了强大的试剂控制，因为底物的固有反应性完全由手性催化剂配合物主导，这表明需要使用阳离子 Rh(I)。该方法可以从简单的起始材料中以高对映选择性快速获得多种 1,2-二氢萘产品。

  DOI：

  10.1021/ja807942m

文献信息

• Biarylmethane and Fused Heterocyclic Arene Synthesis via in Situ Generated <i>o</i>- and/or <i>p</i>-Naphthoquinone Methides
  作者：Yoshinari Sawama、Takahiro Kawajiri、Shota Asai、Naoki Yasukawa、Yuko Shishido、Yasunari Monguchi、Hironao Sajiki

  DOI：10.1021/acs.joc.5b00434

  日期：2015.6.5

  o- and/or p-naphthoquinone methides (NQMs) can be selectively prepared by the ring opening of 1-(siloxymethyl)-1,4-epoxy-1,4-dihydronaphthalene derivatives based on a substituent effect at the 4 position of the substrates. The 4-alkyl- or silyl-substituted 1-(siloxymethyl)-1,4-epoxy-1,4-dihydronaphthalene was transformed to o-NQM (1-naphthoquinone-2-methide), which underwent Friedel–Crafts 1,4-addition

  邻-和/或对-萘醌甲基化物（NQMs）可通过在1-氨基甲氧基-1,4-甲氧基-1,4-环氧-1,4-二氢萘衍生物的开环作用下的1-（甲硅烷氧基甲基）-1,4-环氧-1,4-二氢萘衍生物的开环来选择性地制备。基材。将4-烷基或甲硅烷基取代的1-（甲硅烷氧基甲基）-1,4-环氧-1,4-二氢萘转化为邻-NQM（1-萘醌-2-甲基），然后进行弗里德尔-克拉夫特工艺1,4 -α，β-不饱和羰基部分的加成得到2-苄基-1-萘酚，作为联芳基甲烷，和[4 + 2]-环加成与二烯亲和剂，得到稠合的杂环芳烃。同时，可通过Friedel-Crafts 1,6-加成p的方法将4-未取代的1-（甲硅烷氧基甲基）-1,4-环氧-1,4-二氢萘转化为相应的4-苄基-1-萘酚。-NQM（1-萘醌-4-甲基化物）是通过1,4-环氧部分的位点选择性开环生成的。此外，将4-（甲硅烷氧基甲基）-（1,4-双（甲硅烷氧基甲基））-1
• Conformational Effects in Diastereoselective Aryne Diels−Alder Reactions: Synthesis of Benzo-Fused [2.2.1] Heterobicycles
  作者：Robert Webster、Mark Lautens

  DOI：10.1021/ol9019869

  日期：2009.10.15

  It was found that the diastereoselectivity of the Diels-Alder reaction between arynes and substituted furans is highly sensitive to substitution, which affects the reactive conformation. By varying the location of the groups on the diene partner, it is possible to obtain both excellent chemical yields and high stereoselectivity. This methodology offers rapid and convenient access to enantiomerically pure bicyclic scaffolds which are difficult to prepare by other means.
• Reagent-Controlled Regiodivergent Resolution of Unsymmetrical Oxabicyclic Alkenes Using a Cationic Rhodium Catalyst
  作者：Robert Webster、Christian Böing、Mark Lautens

  DOI：10.1021/ja807942m

  日期：2009.1.21

  nucleophiles to racemic oxabicyclic alkenes produces good yields of regioisomeric products each in high ee. Powerful reagent control is demonstrated, as the inherent reactivity of the substrate is completely dominated by the chiral catalyst complex, which is shown to require the use of cationic Rh(I). The process affords rapid access to multiple 1,2-dihydronapthalene products in high enantioselectivity from simple

  Rh(I) 催化的杂原子亲核试剂向外消旋氧杂双环烯烃的区域发散加成产生了高 ee 的区域异构产物的良好产率。证明了强大的试剂控制，因为底物的固有反应性完全由手性催化剂配合物主导，这表明需要使用阳离子 Rh(I)。该方法可以从简单的起始材料中以高对映选择性快速获得多种 1,2-二氢萘产品。