2-methylbut-3-enyl methanesulfonate | 105698-66-6

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 有机磺酸及其衍生物
• 英文名称: 2-methylbut-3-enyl methanesulfonate
• 英文别名: 2-methyl-3-butenyl-1-mesylate；2-methyl-3-butenyl methanesulfonate；2-methylbut-3-en-1-yl methanesulfonate
• CAS: 105698-66-6
• 化学式: C₆H₁₂O₃S
• 分子量: 164.225
• InChiKey: FGGJRBXVNNTKGO-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.1
• 重原子数：
  10
• 可旋转键数：
  4
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.67
• 拓扑面积：
  51.8
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  2-methylbut-3-enyl methanesulfonate 在 氢氧化钾 、 双氧水 作用下， 以 甲醇 为溶剂， 反应 24.0h， 以4%的产率得到2-methylbut-3-enyl hydroperoxide
  参考文献：
  名称：

  氧化金属化。第24部分。通过不饱和氢过氧化物的环过氧汞化制备环状过氧化物。

  摘要：

  通过用乙酸汞（II）和/或硝酸汞（II）处理，已将十七种不饱和氢过氧化物转化为十九种新的汞化环状过氧化物，随后通过与碱性硼氢化钠的脱汞反应，分离出六种新的无汞过氧化物。结果大大扩展了此类反应的范围，并提供了有关几种不同形式的环过氧汞化的立体选择性和相对难易程度的信息。建议与乙酸汞（II）的反应是动力学控制的，而与硝酸汞（II）的反应表明是产物分布的热力学控制的组成部分。

  DOI：

  10.1016/s0040-4020(01)86350-x
• 作为产物：
  描述：

  2-甲基-3-丁烯酸 在 吡啶 、 lithium aluminium tetrahydride 作用下， 生成 2-methylbut-3-enyl methanesulfonate
  参考文献：
  名称：

  氧化金属化。第24部分。通过不饱和氢过氧化物的环过氧汞化制备环状过氧化物。

  摘要：

  通过用乙酸汞（II）和/或硝酸汞（II）处理，已将十七种不饱和氢过氧化物转化为十九种新的汞化环状过氧化物，随后通过与碱性硼氢化钠的脱汞反应，分离出六种新的无汞过氧化物。结果大大扩展了此类反应的范围，并提供了有关几种不同形式的环过氧汞化的立体选择性和相对难易程度的信息。建议与乙酸汞（II）的反应是动力学控制的，而与硝酸汞（II）的反应表明是产物分布的热力学控制的组成部分。

  DOI：

  10.1016/s0040-4020(01)86350-x

文献信息

• [EN] COMPOUNDS THAT INHIBIT MCL-1 PROTEIN<br/>[FR] COMPOSÉS INHIBANT LA PROTÉINE MCL-1
  申请人：AMGEN INC

  公开号：WO2017147410A1

  公开（公告）日：2017-08-31

  Provided herein are myeloid cell leukemia 1 protein (Mcl-1) inhibitors, methods of their preparation, related pharmaceutical compositions, and methods of using the same. For example, provided herein are compounds of Formula I, and pharmaceutically acceptable salts thereof and pharmaceutical compositions containing the compounds. The compounds and compositions provided herein may be used, for example, in the treatment of diseases or conditions, such as cancer.

  本文提供了髓样细胞白血病1蛋白（Mcl-1）抑制剂，其制备方法，相关的药物组合物，以及使用这些物质的方法。例如，本文提供了化合物I的公式，及其药用盐和含有这些化合物的药物组合物。本文提供的化合物和组合物可以用于治疗癌症等疾病或症状。
• Electrophilic Sulfur Reagent Design Enables Directed <i>syn</i>-Carbosulfenylation of Unactivated Alkenes
  作者：Zi-Qi Li、Yilin Cao、Taeho Kang、Keary M. Engle

  DOI：10.1021/jacs.1c13252

  日期：2022.4.27

  A multi-component approach to structurally complex organosulfur products is described via the nickel-catalyzed 1,2-carbosulfenylation of unactivated alkenes with organoboron nucleophiles and tailored organosulfur electrophiles. The key to the development of this transformation is the identification of a modular N-alkyl-N-(arylsulfenyl)arenesulfonamide family of sulfur electrophiles. Tuning the electronic

  通过镍催化的未活化烯烃与有机硼亲核试剂和定制的有机硫亲电试剂的 1,2-羰基化，描述了一种结构复杂的有机硫产品的多组分方法。开发这种转化的关键是鉴定硫亲电子试剂的模块化N-烷基-N- (芳基亚磺基)芳基磺酰胺家族。通过计算研究检查，调整这些试剂中离去基团的电子和空间特性可控制途径选择性，有利于三组分偶联和抑制副反应。独特的syn-立体选择性不同于传统的涉及硫杂鎓离子中间体的亲电子硫基转移过程，它源于定向的芳基镍 (I) 迁移插入机制，正如通过反应动力学和对照实验所阐明的那样。一系列单齿、弱配位的天然导向基团（包括磺胺、醇、胺、酰胺和氮杂杂环）促进了反应性和区域选择性。
• Alkene 1,3‐Difluorination via Transient Oxonium Intermediates
  作者：Alice C. Dean、E. Harvey Randle、Andrew J. D. Lacey、Guilherme A. Marczak Giorio、Sayad Doobary、Benjamin D. Cons、Alastair J. J. Lennox

  DOI：10.1002/anie.202404666

  日期：2024.7.22

  diastereoselective hypervalent iodine-mediated 1,3-difluorination of homoallylic (aryl) ethers. The transformation proceeds through a transiently formed oxonium intermediate that is opened by fluoride to rearrange an alkyl chain. The protocol is scalable and tolerates a variety of functional groups and substitution on the alkenyl chain. Mechanistic studies reveal key insights into the reaction selectivity.

  我们报道了高烯丙基（芳基）醚的非对映选择性高价碘介导的 1,3-二氟化。该转化通过瞬时形成的氧鎓中间体进行，该中间体被氟化物打开以重新排列烷基链。该协议具有可扩展性，可容忍烯基链上的各种官能团和取代。机理研究揭示了反应选择性的关键见解。
• Regiochemical and stereochemical studies on halocyclization reactions of unsaturated sulfides
  作者：Xiao-Feng Ren、Edward Turos、Charles H. Lake、Melvyn Rowen Churchill

  DOI：10.1021/jo00125a038

  日期：1995.10

  The regiochemistry and stereochemistry for the halocyclization reactions of unsaturated benzyl sulfides have been examined as a function of tether length, type of unsaturation (carbon-carbon double bond versus carbon-carbon triple bond), substituents, and halogenating agent. Alkenyl sulfides were found to react with iodine or bromine at room temperature to give five-membered ring cycloadducts exclusively over those having four-membered rings, while for larger systems, six-membered ring products are formed preferentially over their five-membered ring isomers and exclusively over the seven-membered ring adducts. The endo- versus exo-regioselectivity of these alkenyl sulfide ring closures most likely reflects the difference in thermodynamic stabilities of the beta-halo sulfide cycloadducts, which are able to equilibrate via a common episulfonium intermediate. The efficiency of the cyclization process markedly drops off for these alkenyl sulfides as the tether length increases beyond four intervening carbon centers. Thus, while the halogenations of 3-butenyl sulfides and 4-pentenyl sulfides give high yields of cycloadducts, those of 5-hexenyl sulfides afford only small amounts of cyclized products and large quantities of acyclic dibromides. Conversely the reactions of acetylenic sulfides with iodine give uniformly high yields and regiochemical control regardless of the tether length. Thus, 3-butynyl and 4-pentynyl sulfides cyclize cleanly to the five-membered ring while 5-hexynyl sulfides give exclusively the six-membered ring, The products arising from these alkynyl sulfide ring closures are believed to be formed under kinetic control. The methodology has been applied to the synthesis of unusual bicyclic beta-lactams related to the penicillin family of antibiotics.
• Structure−Activity Relationships at the 5-Position of Thiolactomycin:  An Intact (5<i>R</i>)-Isoprene Unit Is Required for Activity against the Condensing Enzymes from <i>Mycobacterium </i><i>t</i><i>uberculosis</i> and <i>Escherichia </i><i>c</i><i>oli</i>
  作者：Pilho Kim、Yong-Mei Zhang、Gautham Shenoy、Quynh-Anh Nguyen、Helena I. Boshoff、Ujjini H. Manjunatha、Michael B. Goodwin、John Lonsdale、Allen C. Price、Darcie J. Miller、Ken Duncan、Stephen W. White、Charles O. Rock、Clifton E. Barry、Cynthia S. Dowd

  DOI：10.1021/jm050825p

  日期：2006.1.1

  Thiolactomycin inhibits bacterial cell growth through inhibition of the beta-ketoacyl-ACP synthase activity of type II fatty acid synthases. The effect of modifications of the 5-position isoprenoid side chain on both IC(50) and MIC were determined. Synthesis and screening of a structurally diverse set of 5-position analogues revealed very little tolerance for substitution in purified enzyme assays, but a few analogues retained MIC, presumably through another target. Even subtle modifications such as reducing one or both double bonds of the diene were not tolerated. The only permissible structural modifications were removal of the isoprene methyl group or addition of a methyl group to the terminus. Cocrystallization of these two inhibitors with the condensing enzyme from Escherichia coli revealed that they retained the TLM binding mode at the active site with reduced affinity. These results suggest a strict requirement for a conjugated, planar side chain inserting within the condensing enzyme active site.