2,4-dimethoxybenzyl thiotosylate | 180712-44-1

• 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: 2,4-dimethoxybenzyl thiotosylate
• 英文别名: S-2,4-dimethoxybenzyl toluenethiosulfonate；S-(2,4-dimethoxybenzyl)-4-methylbenzenesulfonothioate；2,4-Dimethoxy-1-[(4-methylphenyl)sulfonylsulfanylmethyl]benzene
• CAS: 180712-44-1
• 化学式: C₁₆H₁₈O₄S₂
• 分子量: 338.449
• InChiKey: DCLAVQFMLMLZFY-UHFFFAOYSA-N

物化性质

• 沸点：
  492.1±55.0 °C(Predicted)
• 密度：
  1.252±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.4
• 重原子数：
  22
• 可旋转键数：
  6
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.25
• 拓扑面积：
  86.3
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  2,4-dimethoxybenzyl thiotosylate 在 四氢吡咯 、 四(三苯基膦)钯 、 三苯基膦 、 lithium hexamethyldisilazane 作用下， 以 二氯甲烷 为溶剂， 反应 3.5h， 生成 (2R,3R)-2-Allyloxycarbonylamino-3-(2,4-dimethoxy-benzylsulfanyl)-succinic acid 4-(4-methoxy-benzyl) ester
  参考文献：
  名称：

  Electrophilic sulfenylation in a stereocontrolled synthesis of protected (2R,3R)-3-mercaptoaspartic acid from -aspartic acid

  摘要：

  A novel electrophilic sulfenylating agent, (2,4-dimethoxybenzylthio)-4-methylphenyl sulfonate (13) was developed to give thiols bearing an acid labile protecting group. This was subsequently used to prepare in a stereocontrolled manner, a protected form of (2R,3R)-3-mercaptoaspartic acid which was incorporated into a tripeptide. Copyright (C) 1996 Published by Elsevier Science Ltd

  DOI：

  10.1016/0040-4020(96)00765-x
• 作为产物：
  描述：

  2,4-二甲氧基苄醇 在 三乙胺 作用下， 以 二氯甲烷 、 丙酮 为溶剂， 反应 18.08h， 生成 2,4-dimethoxybenzyl thiotosylate
  参考文献：
  名称：

  Electrophilic sulfenylation in a stereocontrolled synthesis of protected (2R,3R)-3-mercaptoaspartic acid from -aspartic acid

  摘要：

  A novel electrophilic sulfenylating agent, (2,4-dimethoxybenzylthio)-4-methylphenyl sulfonate (13) was developed to give thiols bearing an acid labile protecting group. This was subsequently used to prepare in a stereocontrolled manner, a protected form of (2R,3R)-3-mercaptoaspartic acid which was incorporated into a tripeptide. Copyright (C) 1996 Published by Elsevier Science Ltd

  DOI：

  10.1016/0040-4020(96)00765-x

文献信息

• Thiazolidine-Protected β-Thiol Asparagine: Applications in One-Pot Ligation–Desulfurization Chemistry
  作者：Jessica Sayers、Robert E. Thompson、Kristen J. Perry、Lara R. Malins、Richard J. Payne

  DOI：10.1021/acs.orglett.5b02468

  日期：2015.10.2

  The synthesis of a β-thiol asparagine derivative bearing a novel (2,4,6-trimethoxyphenyl)thiazolidine protecting group is described. The efficient incorporation of the amino acid into the N-termini of peptides is demonstrated as well as the utility of the β-thiol asparagine moiety for rapid ligation reactions with peptide thioesters. The streamlined synthesis of native peptide products could be accomplished

  描述了带有新的（2,4,6-三甲氧基苯基）噻唑烷保护基的β-硫醇天冬酰胺衍生物的合成。证明了将氨基酸有效地掺入肽的N-末端以及将β-硫醇天冬酰胺部分用于与肽硫酯的快速连接反应的效用。连接事件发生后，可以使用β-硫醇助剂的一锅自由基脱硫来完成天然肽产物的简化合成。氨基酸的实用性在HIV进入抑制剂恩夫韦肽的高效一锅组装中得到了强调。
• A novel base-induced cyclization of selected benzyl alkynyl sulfides for the synthesis of 2-aryl-2,3-dihydrothiophenes
  作者：Laura K McConachie、Adrian L Schwan

  DOI：10.1016/s0040-4039(00)00916-3

  日期：2000.7

  2-Halobenzyl 1-alkynyl sulfides undergo an unprecedented dihydrothiophene formation when treated with 2 equiv. of KOtBu in CH3CN. The reaction, believed to proceed via a 5-endo-dig cyclization, is sluggish or non-existent in the absence of the halogen.

  当用2当量处理时，2-卤代苄基1-炔基硫化物经历前所未有的二氢噻吩形成。CH 3 CN中KO t Bu的摩尔数。据信该反应是通过5-内挖-环化进行的，在没有卤素的情况下反应缓慢或不存在。
• Peptide Ligation
  申请人：THE UNIVERSITY OF SYDNEY

  公开号：US20160122383A1

  公开（公告）日：2016-05-05

  The invention relates to a process for introducing a thiol group a to a carbonyl group in a side chain of a protected a-amino acid, said protected a-amino acid having protecting groups on both the α-amine group and the a-carboxyl group. The process comprises a) if the side chain contains a functional group comprising a heteroatom bearing a hydrogen atom, protecting said functional group; b) treating the protected amino acid with a base of sufficient strength to abstract a hydrogen atom a to the carbonyl group, so as to form an anion; c) treating the anion with a reagent of structure Pr-S-L in which L is a leaving group and Pr is a thiol-protecting group, so as to introduce a Pr-S- group a to the carbonyl group; and d) converting the Pr-S- group to an H-S-(thiol) group. This process may be used to prepare ligated peptides.

  该发明涉及一种将巯基引入受保护的α-氨基酸侧链中的羰基的过程，所述受保护的α-氨基酸在α-氨基团和α-羧基团上均具有保护基。该过程包括a) 如果侧链含有包含带有氢原子的杂原子的官能团，则保护该官能团；b) 用足够强度的碱处理受保护的氨基酸，以提取到羰基的氢原子，从而形成负离子；c) 用具有结构Pr-S-L的试剂处理该负离子，其中L是一个离去基团，Pr是一个巯基保护基，以引入Pr-S-基团到羰基；d) 将Pr-S-基团转化为H-S-(巯基)基团。该过程可用于制备连接的肽。
• Thiolation and Carboxylation of Glutathione Synergistically Enhance Its Lead-Detoxification Capabilities
  作者：Luca Sauser、Tagwa A. Mohammed、Tadeáš Kalvoda、Sheng-Jan Feng、Bernhard Spingler、Lubomír Rulíšek、Michal S. Shoshan

  DOI：10.1021/acs.inorgchem.1c03030

  日期：2021.12.20

  Yet, although weakly binding the poisonous metal lead (Pb), GSH poorly detoxifies it. β-Mercaptoaspartic acid is a new-to-nature novel amino acid that was found to enhance the Pb-detoxification capability of a synthetic cyclic tetrapeptide. Aiming to explore the advantages of noncanonical amino acids (ncAAs) of this nature, we studied the detoxification capabilities of GSH and three analogue peptides

  天然三肽谷胱甘肽 (GSH) 是一种普遍存在的化合物，具有多种生物学功能，其中包括与必需金属离子和有毒金属离子相互作用。然而，虽然谷胱甘肽与有毒金属铅 (Pb) 的结合较弱，但其解毒效果却很差。 β-巯基天冬氨酸是一种全新的氨基酸，被发现可以增强合成环状四肽的铅解毒能力。为了探索这种性质的非规范氨基酸 (ncAA) 的优势，我们研究了 GSH 和三种类似肽的解毒能力，每种肽均含有至少一种同时含有游离羧酸根和硫醇根基团的 ncAA。一项彻底的研究，包括体外解毒和机制评估、金属结合亲和力、金属选择性和计算研究表明，这些 ncAA 在额外增强 Pb 结合方面非常有益，并揭示了高亲和力和金属选择性在协同减少 Pb 方面的重要性细胞毒性。因此，此类 ncAA 加入了对抗铅中毒和污染的化学工具箱，使肽能够强烈且选择性地结合有毒金属离子。
• One-Pot Peptide Ligation–Desulfurization at Glutamate
  作者：Katie M. Cergol、Robert E. Thompson、Lara R. Malins、Peter Turner、Richard J. Payne

  DOI：10.1021/ol403288n

  日期：2014.1.3

  steps from protected glutamic acid and could be incorporated at the N-terminus of peptides. The application of these peptides in one-pot ligation–desulfurization chemistry is demonstrated with a range of peptide thioesters, and the utility of this methodology is highlighted through the synthesis of the osteoporosis peptide drug teriparatide (Forteo).

  描述了一种在谷氨酸（Glu）上连接的有效方法。从受保护的谷氨酸仅需三步即可获得γ-硫醇-Glu构建基块，并且可以将其掺入肽段的N端。一系列肽硫酯证明了这些肽在一锅连接-脱硫化学中的应用，并且通过合成骨质疏松症肽药物特立帕肽（Forteo）突出了该方法的实用性。