o-nitrobenzyl methylthiomethyl ether | 500776-06-7

• 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: o-nitrobenzyl methylthiomethyl ether
• 英文别名: 1-(Methylsulfanylmethoxymethyl)-2-nitrobenzene；1-(methylsulfanylmethoxymethyl)-2-nitrobenzene
• CAS: 500776-06-7
• 化学式: C₉H₁₁NO₃S
• 分子量: 213.257
• InChiKey: LRAKDULCULOGMQ-UHFFFAOYSA-N

物化性质

• 沸点：
  302.4±27.0 °C(Predicted)
• 密度：
  1.247±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.5
• 重原子数：
  14
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.33
• 拓扑面积：
  80.4
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  o-nitrobenzyl methylthiomethyl ether 在 2,2,6,6-四甲基哌啶氧化物 、 碘苯二乙酸 、 二异丁基氢化铝 、 盐酸-N-乙基-Nˊ-(3-二甲氨基丙基)碳二亚胺 、 copper(I) bromide 作用下， 以 二氯甲烷 、 水 、 乙腈 为溶剂， 反应 44.67h， 生成
  参考文献：
  名称：

  Substrate Controlled Divergence in Polyketide Synthase Catalysis

  摘要：

  Biochemical characterization of polyketide synthases (PKSs) has relied on synthetic substrates functionalized as electrophilic esters to acylate the enzyme and initiate the catalytic cycle. In these efforts, N-acetylcysteamine thioesters have typically been employed for in vitro studies of full PKS modules as well as excised domains. However, substrate engineering approaches to control the catalytic cycle of a full PKS module harboring multiple domains remain underexplored. This study examines a series of alternatively activated native hexaketide substrates on the catalytic outcome of PikAIV, the sixth and final module of the pikromycin (Pik) pathway. We demonstrate the ability to control product formation with greater than 10:1 selectivity for either full module catalysis, leading to a 14-membered macrolactone, or direct cyclization to a 12-membered ring. This outcome was achieved through modifying the type of hexaketide ester employed, demonstrating the utility of substrate engineering in PKS functional studies and biocatalysis.

  DOI：

  10.1021/ja511743n
• 作为产物：
  描述：

  邻硝基苯甲醇 、 二甲基亚砜 在 乙酸酐 、 溶剂黄146 作用下， 以 水 为溶剂， 反应 74.0h， 以72%的产率得到o-nitrobenzyl methylthiomethyl ether
  参考文献：
  名称：

  从受保护的 TPA 亚磷酰胺构建块合成的自旋标记核糖开关

  摘要：

  硝基氧 TPA（2,2,5,5-四甲基-吡咯啉-1-氧基-3-乙炔）已受到光敏 2-NBOM 基团的保护，并连接到尿苷亚磷酰胺结构单元。自旋标记的 RNA 可以通过寡核苷酸合成的标准方案从该化合物中获得，并用于光诱导脱保护后的 EPR 研究。

  DOI：

  10.1002/chem.202201822

文献信息

• Photochemistry of 2-Nitrobenzyl Enol Ethers:  Oxidative CC Bond Scission
  作者：Promise K. Yong、Anamitro Banerjee

  DOI：10.1021/ol0508072

  日期：2005.6.1

  [reaction: see text] 2-Nitrobenzyl enol ethers, when photolyzed in the presence of air, result in an oxidative C=C bond scission, forming a ketone as the major product (>60% yield). Enol release leads to the aldehyde as the minor product.

  [反应：见正文] 2-硝基苄基烯醇醚在空气中光解时会导致C = C氧化键断裂，形成酮类为主产物（收率> 60％）。烯醇的释放导致醛为次要产物。
• A Cytidine Phosphoramidite with Protected Nitroxide Spin Label: Synthesis of a Full-Length TAR RNA and Investigation by In-Line Probing and EPR Spectroscopy
  作者：Timo Weinrich、Eva A. Jaumann、Ute Scheffer、Thomas F. Prisner、Michael W. Göbel

  DOI：10.1002/chem.201800167

  日期：2018.4.20

  to the chemical nature of nitroxide spin labels: Decomposition while oligonucleotides are chemically synthesized, further decay during enzymatic strand ligation, and undetected changes in conformational equilibria due to the steric demand of the label. Herein possible solutions for all three problems are presented: A 2‐nitrobenzyloxymethyl protective group for nitroxides that is stable under all conditions

  对RNA的EPR研究由于与三氧化氮自旋标记的化学性质有关的三个主要障碍而变得复杂：寡核苷酸是化学合成的分解，在酶链连接过程中进一步降解，以及由于标记的空间需求而未检测到的构象平衡变化。本文提出了针对所有三个问题的可能解决方案：用于硝基氧的2-硝基苄氧基甲基保护基团，在化学RNA合成的所有条件下均稳定，并且可以光化学方式除去。通过仔细选择连接位点和夹板寡核苷酸，在装配有两个受保护的氮氧化物基团的全长HIV-1 TAR RNA的组装中实现了高产量。在不存在和存在精氨酸酰胺的情况下，对自旋标记的TAR的PELDOR测量表明，配体结合的螺旋间运动被阻止。最终，通过在线探测，即使是自旋标记的存在，即使构象上的微小变化都可以被高灵敏度地检测到。
• DETEKTION VON WECHSELWIRKUNGEN AUF SONDEN-ARRAYS
  申请人：Clondiag Chip Technologies GmbH

  公开号：EP1425417B1

  公开（公告）日：2007-10-31
• Substrate Controlled Divergence in Polyketide Synthase Catalysis
  作者：Douglas A. Hansen、Aaron A. Koch、David H. Sherman

  DOI：10.1021/ja511743n

  日期：2015.3.25

  Biochemical characterization of polyketide synthases (PKSs) has relied on synthetic substrates functionalized as electrophilic esters to acylate the enzyme and initiate the catalytic cycle. In these efforts, N-acetylcysteamine thioesters have typically been employed for in vitro studies of full PKS modules as well as excised domains. However, substrate engineering approaches to control the catalytic cycle of a full PKS module harboring multiple domains remain underexplored. This study examines a series of alternatively activated native hexaketide substrates on the catalytic outcome of PikAIV, the sixth and final module of the pikromycin (Pik) pathway. We demonstrate the ability to control product formation with greater than 10:1 selectivity for either full module catalysis, leading to a 14-membered macrolactone, or direct cyclization to a 12-membered ring. This outcome was achieved through modifying the type of hexaketide ester employed, demonstrating the utility of substrate engineering in PKS functional studies and biocatalysis.
• Spin‐Labeled Riboswitch Synthesized from a Protected TPA Phosphoramidite Building Block
  作者：Frank Kaiser、Burkhard Endeward、Alberto Collauto、Ute Scheffer、Thomas F. Prisner、Michael W. Göbel

  DOI：10.1002/chem.202201822

  日期：2022.10.7

  nitroxide TPA (2,2,5,5-tetramethyl-pyrrolin-1-oxyl-3-acetylene) has been protected with a light sensitive 2-NBOM group and connected to a uridine phosphoramidite building block. Spin-labeled RNA can be obtained from this compound by standard protocols of oligonucleotide synthesis and used for EPR studies after light-induced deprotection.

  硝基氧 TPA（2,2,5,5-四甲基-吡咯啉-1-氧基-3-乙炔）已受到光敏 2-NBOM 基团的保护，并连接到尿苷亚磷酰胺结构单元。自旋标记的 RNA 可以通过寡核苷酸合成的标准方案从该化合物中获得，并用于光诱导脱保护后的 EPR 研究。