(R)-1-vinylisochromane

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 苯并吡喃
• 英文名称: (R)-1-vinylisochromane
• 英文别名: (1R)-1-ethenyl-3,4-dihydro-1H-isochromene
• 化学式: C₁₁H₁₂O
• 分子量: 160.216
• InChiKey: OABXVWUBTBVCCP-LLVKDONJSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.5
• 重原子数：
  12
• 可旋转键数：
  1
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.27
• 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：

  (R)-1-vinylisochromane 在 sodium tetrahydroborate 、 臭氧 作用下， 生成 (S)-1-Isochroman-1-yl-methanol
  参考文献：
  名称：

  External chiral ligand-induced enantioselective lithiation/SE2 reactions of isochroman and phthalan

  摘要：

  Treatment of isochroman and phthalan with a t-BuLi/chiral bis(oxazoline) complex followed by reaction with carbon-electrophiles such as benzaldehyde and CO2 is shown to afford the a-substituted derivatives in moderate-to-high enantioselectivities (up to 97% ee and 83% ee, respectively). The asymmetric induction is proved to occur at the post-lithiation step. (C) 2000 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0040-4039(00)01028-5
• 作为产物：
  描述：

  异色满 在 lithium aluminium tetrahydride 、 敌草腈 、 叔丁基锂 、 (4S,4′S)-(-)-2,2′-(3-戊烯基)双(4-异丙基噁唑啉) 作用下， 以 正己烷 为溶剂， 反应 2.5h， 生成 (R)-1-vinylisochromane
  参考文献：
  名称：

  External chiral ligand-induced enantioselective lithiation/SE2 reactions of isochroman and phthalan

  摘要：

  Treatment of isochroman and phthalan with a t-BuLi/chiral bis(oxazoline) complex followed by reaction with carbon-electrophiles such as benzaldehyde and CO2 is shown to afford the a-substituted derivatives in moderate-to-high enantioselectivities (up to 97% ee and 83% ee, respectively). The asymmetric induction is proved to occur at the post-lithiation step. (C) 2000 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0040-4039(00)01028-5

文献信息

• Sulfoxide ligand metal catalyzed oxidation of olefins
  申请人：The Board of Trustees of the University of Illinois

  公开号：US10266503B1

  公开（公告）日：2019-04-23

  The enantioselective synthesis of isochroman motifs has been accomplished via Pd(II)-catalyzed allylic C—H oxidation from terminal olefin precursors. Critical to the success of this goal was the development and utilization of a novel chiral aryl sulfoxide-oxazoline (ArSOX) ligand. The allylic C—H oxidation reaction proceeds with the broadest scope and highest levels asymmetric induction reported to date (avg. 92% ee, 13 examples ≥90% ee). Additionally, C(sp3)-N fragment coupling reaction between abundant terminal olefins and N-triflyl protected aliphatic and aromatic amines via Pd(II)/sulfoxide (SOX) catalyzed intermolecular allylic C—H amination is disclosed. A range of 52 allylic amines are furnished in good yields (avg. 76%) and excellent regio- and stereoselectivity (avg. >20:1 linear:branched, >20:1 E:Z). For the first time, a variety of singly activated aromatic and aliphatic nitrogen nucleophiles, including ones with stereochemical elements, can be used in fragment coupling stiochiometries for intermolecular C—H amination reactions.

  通过Pd(II)-催化的烯烃末端前体的烯丙基C—H氧化，已经实现了对异色烷基苯并环的对映选择性合成。这一目标的成功关键在于开发和利用一种新型手性芳基亚砜-噁唑啉（ArSOX）配体。烯丙基C—H氧化反应具有迄今报道的最广泛范围和最高水平的不对称诱导（平均92% ee，13个例子≥90% ee）。此外，通过Pd(II)/亚砜（SOX）催化的分子间烯丙基C—H胺化揭示了丰富的末端烯烃和N-三氟甲磺酰保护的脂肪族和芳香族胺之间的C(sp3)-N片段偶联反应。一系列52种烯丙基胺以良好的产率（平均76%）和优异的区域和立体选择性（平均>20:1线性:支链，>20:1 E:Z）提供。首次，各种单独活化的芳香族和脂肪族氮亲核试剂，包括具有立体化学元素的试剂，可以在分子间C—H胺化反应的片段偶联化学计量中使用。
• Enantioselective Allylic C−H Oxidation of Terminal Olefins to Isochromans by Palladium(II)/Chiral Sulfoxide Catalysis
  作者：Stephen E. Ammann、Wei Liu、M. Christina White

  DOI：10.1002/anie.201603576

  日期：2016.8.8

  The enantioselective synthesis of isochroman motifs has been accomplished by palladium(II)‐catalyzed allylic C−H oxidation from terminal olefin precursors. Critical to the success of this goal was the development and utilization of a novel chiral aryl sulfoxide‐oxazoline (ArSOX) ligand. The allylic C−H oxidation reaction proceeds with the broadest scope and highest levels of asymmetric induction reported

  对异氰酸酯基序的对映选择性合成已通过钯（II）催化烯基CH从末端烯烃前体的氧化而完成。实现这一目标的关键是开发和利用新型手性芳基亚砜-恶唑啉（ArSOX）配体。与最宽的范围和不对称诱导最高水平的烯丙基C-H的氧化反应的进行报告的日期（平均92％ee值，13点的例子具有大于90％的ee值）。
• Asymmetric Dehydrative C-, N-, and O-Allylation Using Naph-diPIM-dioxo-i-Pr-CpRu/p-TsOH Combined Catalyst
  作者：Masato Kitamura、Kengo Miyata

  DOI：10.1055/s-0031-1290301

  日期：2012.7

  synthetic process can be readily scaled up. (S,S)- or (R,R)-Naph-diPIM-dioxo-i-Pr–CpRu(II) complex with a Brønsted acid catalyzes dehydrative intermolecular C-allylation with high enantio- and regioselectivity. The new soft Ru/hard H+ combined catalyst can also be used for intramolecular C-, N-, and O-allylations, giving nearly enantiomerically pure α-alkenyl-substituted cyclic compounds. As water is only

  摘要 （S，S）-或（R，R）-Naph-diPIM-dioxo- i -Pr-CpRu（II）配合物与布朗斯台德酸催化脱水的分子间C-烯丙基化，具有高对映体和区域选择性。新型软Ru /硬H +混合催化剂还可用于分子内C-，N-和O-烯丙基化，生成几乎对映体纯的α-烯基取代的环状化合物。由于水只是副产品，因此合成工艺可以轻松扩大规模。 （S，S）-或（R，R）-Naph-diPIM-dioxo- i -Pr-CpRu（II）配合物与布朗斯台德酸催化脱水的分子间C-烯丙基化，具有高对映体和区域选择性。新型软Ru /硬H +混合催化剂还可用于分子内C-，N-和O-烯丙基化，生成几乎对映体纯的α-烯基取代的环状化合物。由于水只是副产品，因此合成工艺可以轻松扩大规模。
• A Chiral Bidentate sp2-N Ligand, Naph-diPIM: Application to CpRu-Catalyzed Asymmetric Dehydrative C-, N-, and O-Allylation
  作者：Kengo Miyata、Hironori Kutsuna、Sho Kawakami、Masato Kitamura

  DOI：10.1002/anie.201100772

  日期：2011.5.9
• JP5747321
  申请人：——

  公开号：——

  公开（公告）日：——