3-(p-toluenesulfonyloxy)-2-cyclopenten-1-one | 205999-79-7

• 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: 3-(p-toluenesulfonyloxy)-2-cyclopenten-1-one
• 英文别名: 3-oxocyclopent-1-en-1-yl 4-methylbenzenesulfonate；(3-Oxocyclopenten-1-yl) 4-methylbenzenesulfonate；(3-oxocyclopenten-1-yl) 4-methylbenzenesulfonate
• CAS: 205999-79-7
• 化学式: C₁₂H₁₂O₄S
• 分子量: 252.291
• InChiKey: DUNMIVQLQNMUET-UHFFFAOYSA-N

物化性质

• 沸点：
  415.2±45.0 °C(Predicted)
• 密度：
  1.35±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.7
• 重原子数：
  17
• 可旋转键数：
  3
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.25
• 拓扑面积：
  68.8
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  3-(p-toluenesulfonyloxy)-2-cyclopenten-1-one 在 盐酸 、 lithium diisopropyl amide 作用下， 以 四氢呋喃 为溶剂， 生成 4-benzylcyclopentane-1,3-dione
  参考文献：
  名称：

  [EN] TARGETED COVALENT PROBES AND INHIBITORS OF PROTEINS CONTAINING REDOX-SENSITIVE CYSTEINES
  [FR] SONDES COVALENTES CIBLÉES ET INHIBITEURS DE PROTÉINES CONTENANT DES CYSTÉINES SENSIBLES À L'OXYDORÉDUCTION

  摘要：

  揭示了用于修饰治疗重要蛋白质（特别是激酶和磷酸酶）的亚硫酰形式（即亚硫酸，RSOH和亚硫酰胺，RSNR'2）的共价、不可逆的小分子抑制剂，其中组合物包括具有取代芳基或杂环核结构的化合物，促进与特定蛋白质的结合相互作用，以及能够与蛋白质中的亚硫酸或亚硫酰胺修饰的半胱氨酸残基形成共价键的亲核反应中心（碳、氮、硫或磷）。还揭示了合成这些化合物的方法，以及使用它们确定包含活性化合物的化学组合物对特定蛋白质的生物活性以及确定抑制剂对特定蛋白质的效力的方法。

  公开号：

  WO2014089546A1
• 作为产物：
  描述：

  1,3-环戊二酮 、 对甲苯磺酰氯 在 三乙胺 作用下， 以 四氢呋喃 为溶剂， 反应 0.17h， 以88%的产率得到3-(p-toluenesulfonyloxy)-2-cyclopenten-1-one
  参考文献：
  名称：

  二级烷基铜试剂与 3-卤代不饱和羰基衍生物的非对映和对映选择性交叉偶联。

  摘要：

  手性仲烷基铜试剂由相应的烷基碘化物制备，并通过使用t BuLi（-100 °C，1 分钟）进行 I/Li 交换，然后与 CuBr ⋅ P(OEt) 3 (-100 ° C，20 秒）。这些立体定义的仲烷基铜与几种 3-碘或 3-溴不饱和羰基衍生物进行立体保持交叉偶联，从而以良好的收率和高非对映选择性（dr 高达 96:4）生成相应的 γ-甲基化迈克尔受体。该方法扩展到对映异构体富集的烷基铜，提供具有高达 90% ee的光学富集的高级天然产物中间体。

  DOI：

  10.1002/chem.202002297

文献信息

• Synthesis of β-triazolylenones via metal-free desulfonylative alkylation of <i>N</i>-tosyl-1,2,3-triazoles
  作者：Soumyaranjan Pati、Renata G Almeida、Eufrânio N da Silva Júnior、Irishi N N Namboothiri

  DOI：10.3762/bjoc.17.66

  日期：——

  N-tosyl-1,2,3-triazoles under metal-free conditions leading to β-triazolylenones is reported here. The present study encompasses the synthesis of triazoles with a new substitution pattern in a single step from cyclic 1,3-dicarbonyl compounds and N-tosyl triazole in moderate to high yields. Our synthesis takes place with complete regioselectivity as confirmed by crystallographic analysis which is rationalized

  在此报道了N-甲苯磺酰基-1,2,3-三唑在无金属条件下的脱磺酰基烷基化反应，生成β-三唑烯酮。本研究涵盖了从环状1,3-二羰基化合物和N-甲苯磺酰基三唑以中等至高收率一步合成具有新取代模式的三唑。如晶体学分析所证实的那样，我们的合成具有完全的区域选择性，该晶体学分析通过适当的机械方案被合理化。该方法为合成新的功能化1,2,3-三唑提供了有效，通用和直接的策略。
• Rhodium-Catalyzed Asymmetric 1,6-Addition of Aryltitanates to Enynones Giving Axially Chiral Allenes
  作者：Tamio Hayashi、Norihito Tokunaga、Kazuya Inoue

  DOI：10.1021/ol036309f

  日期：2004.1.1

  [GRAPHICS]The addition of aryltitanate reagents ArTi(OPr-i)(4)Li to 3-alkynyl-2-en-1-ones in the presence of chlorotrimethylsilane and a rhodium-(R)-segphos as a catalyst proceeded in a 1,6-fashion to give a high yield of axially chiral allenylalkenyl silyl enol ethers with up to 93% ee.
• Investigation of the N-Substituent Conformation Governing Potency and μ Receptor Subtype-Selectivity in (+)-(3<i>R</i>,4<i>R</i>)-Dimethyl-4-(3-hydroxyphenyl)- piperidine Opioid Antagonists
  作者：James B. Thomas、S. Wayne Mascarella、Richard B. Rothman、John S. Partilla、Heng Xu、Karen B. McCullough、Christina M. Dersch、Buddy E. Cantrell、Dennis M. Zimmerman、F. Ivy Carroll

  DOI：10.1021/jm980063g

  日期：1998.5.1

  A study of the binding site requirements associated with the N-substituent of (+)-(3R,4R)-dimethyl-4-(3-hydroxyphenyl)piperidine (4) derivatives was undertaken using a set of rigid vs flexible N-substituents. The study showed that compounds 7-9 bearing the trans-cinnamyl N-substituent most closely reproduced the potency at the opioid receptor of the flexible N-propylphenyl or N-propylcyclohexyl analogues previously reported. Neither the N-substituted cis-cinnamyl nor the cis-phenylcyclopropylmethyl compounds 10 and 11, respectively, showed high affinity for the opioid receptor. However, the N-trans-phenylcyclopropylmethyl compound 12 closely approximated the affinity of compounds 7-9. Additionally, we found that free rotation of the phenyl ring is necessary for high affinity binding and mu receptor subtype selectivity as the planar N-substituted thianaphthylmethyl and benzofuranylmethyl compounds 13 and 14 had significantly lower binding affinities. Altogether, these findings suggest that the high binding affinity, selectivity, and antagonist potency of N-propylphenyl or N-propylcyclohexyl analogues of (+)-(3R,4R)-dimethyl-4-(3-hydroxyphenyl) (4) are achieved via a conformation wherein the connecting chain of the N-substituents is extended away from piperidine nitrogen with the appended ring system rotated out-of-plane relative to the connecting chain atoms. This conformation is quite similar to that observed in the solid state for 5, as determined by single crystal X-ray analysis. Additionally, it was found that, unlike naltrexone, N-substituents bearing secondary carbons attached directly to the piperidine nitrogen of 4 suffer dramatic losses of potency vs analogues not substituted in this manner. Using a functional assay which measured stimulation or inhibition of [S-35]GTP-gamma-S binding, we show that the trans-cinnamyl analogues of (+)-(3R,4R)-dimethyl-4-(3-hydroxyphenyl)piperidine (4) retain opioid pure antagonist activity and possess picomolar antagonist potency at the mu receptor.
• [EN] TARGETED COVALENT PROBES AND INHIBITORS OF PROTEINS CONTAINING REDOX-SENSITIVE CYSTEINES<br/>[FR] SONDES COVALENTES CIBLÉES ET INHIBITEURS DE PROTÉINES CONTENANT DES CYSTÉINES SENSIBLES À L'OXYDORÉDUCTION
  申请人：SCRIPPS RESEARCH INST

  公开号：WO2014089546A1

  公开（公告）日：2014-06-12

  Covalent, irreversible small-molecule inhibitors that modify the sulfenyl form (i.e., sulfenic acid, RSOH and sulfenamide, RSNR'2) of therapeutically important proteins (particularly kinases and phosphatases) are disclosed, where the compositions include a compound having a substituted aryl or heterocyclic core structure that promotes binding interactions with a specific protein, and a nucleophilic reaction center (carbon, nitrogen, sulfur, or phosphorous) that is capable of forming a covalent bond with a sulfenic acid- or sulfenamide-modified cysteine residue in the protein. Methods for synthesizing these compounds are also disclosed, as well as methods of using them for determining the bioactivity of a chemical composition comprising an active compound toward a specific protein and for determining the potency of an inhibitor against a specific protein.

  揭示了用于修饰治疗重要蛋白质（特别是激酶和磷酸酶）的亚硫酰形式（即亚硫酸，RSOH和亚硫酰胺，RSNR'2）的共价、不可逆的小分子抑制剂，其中组合物包括具有取代芳基或杂环核结构的化合物，促进与特定蛋白质的结合相互作用，以及能够与蛋白质中的亚硫酸或亚硫酰胺修饰的半胱氨酸残基形成共价键的亲核反应中心（碳、氮、硫或磷）。还揭示了合成这些化合物的方法，以及使用它们确定包含活性化合物的化学组合物对特定蛋白质的生物活性以及确定抑制剂对特定蛋白质的效力的方法。
• Diastereo‐ and Enantioselective Cross‐Couplings of Secondary Alkylcopper Reagents with 3‐Halogeno‐Unsaturated Carbonyl Derivatives
  作者：Alexander Kremsmair、Juri Skotnitzki、Paul Knochel

  DOI：10.1002/chem.202002297

  日期：2020.9.16

  followed by a transmetalation with CuBr⋅P(OEt)3 (−100 °C, 20 s). These stereodefined secondary alkylcoppers underwent stereoretentive cross‐couplings with several 3‐iodo or 3‐bromo unsaturated carbonyl derivatives leading to the corresponding γ‐methylated Michael acceptors in good yields and with high diastereoselectivities (dr up to 96:4). The method was extended to enantiomerically enriched alkylcoppers

  手性仲烷基铜试剂由相应的烷基碘化物制备，并通过使用t BuLi（-100 °C，1 分钟）进行 I/Li 交换，然后与 CuBr ⋅ P(OEt) 3 (-100 ° C，20 秒）。这些立体定义的仲烷基铜与几种 3-碘或 3-溴不饱和羰基衍生物进行立体保持交叉偶联，从而以良好的收率和高非对映选择性（dr 高达 96:4）生成相应的 γ-甲基化迈克尔受体。该方法扩展到对映异构体富集的烷基铜，提供具有高达 90% ee的光学富集的高级天然产物中间体。