2-methyl-3-oxo-5-phenyl-4-pentynethioic acid ethyl ester

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 酮酸及其衍生物
• 英文名称: 2-methyl-3-oxo-5-phenyl-4-pentynethioic acid ethyl ester
• 英文别名: ethyl 2-methyl-3-oxo-5-phenylpent-4-ynoate
• 化学式: C₁₄H₁₄O₃
• 分子量: 230.263
• InChiKey: LAKDEBGQGKZNON-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.2
• 重原子数：
  17
• 可旋转键数：
  5
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.29
• 拓扑面积：
  43.4
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  2-methyl-3-oxo-5-phenyl-4-pentynethioic acid ethyl ester 在 咪唑 、 sodium tetrahydroborate 、 lithium aluminium tetrahydride 、 Noyori's catalyst 、 甲酸 、 四丁基氟化铵 、 三甲基铝 、 diethylzinc 、 palladium diacetate 、 sodium hydride 、 碳酸氢钠 、 戴斯-马丁氧化剂 、 三乙胺 、 三苯基膦 作用下， 以 四氢呋喃 、 甲醇 、 正己烷 、 二氯甲烷 、 乙酸乙酯 、 甲苯 、 苯 为溶剂， 反应 71.75h， 生成 ((3S,4R,5S,6S,E)-3,5-Dimethoxy-4,6-dimethyloct-1-en-7-yn-1-yl)benzene
  参考文献：
  名称：

  Diastereoselective synthesis of an advanced intermediate of the crocacin family using asymmetric transfer hydrogenation-DKR and Marshall allenylation as key reactions

  摘要：

  The natural product of a crocacin-family structural scaffold bearing consecutive anti-anti-syn stereogenic centers was accomplished by means of ATH-DKR and Marshall allenylation reactions with high stereo-control levels. The salient feature of this process is that a single catalytic asymmetric Ru-complex was used for the chirality genesis of pivotal reactions with a high substrate-to-catalyst ratio. (C) 2015 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tet.2015.09.057
• 作为产物：
  描述：

  苯乙炔 在 正丁基锂 、 lithium diisopropyl amide 作用下， 以 四氢呋喃 、 正己烷 、 环己烷 为溶剂， 反应 4.08h， 生成 2-methyl-3-oxo-5-phenyl-4-pentynethioic acid ethyl ester
  参考文献：
  名称：

  Diastereoselective synthesis of an advanced intermediate of the crocacin family using asymmetric transfer hydrogenation-DKR and Marshall allenylation as key reactions

  摘要：

  The natural product of a crocacin-family structural scaffold bearing consecutive anti-anti-syn stereogenic centers was accomplished by means of ATH-DKR and Marshall allenylation reactions with high stereo-control levels. The salient feature of this process is that a single catalytic asymmetric Ru-complex was used for the chirality genesis of pivotal reactions with a high substrate-to-catalyst ratio. (C) 2015 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tet.2015.09.057

文献信息

• Novel Oxygenations with IBX
  作者：Alexander Duschek、Stefan F. Kirsch

  DOI：10.1002/chem.200901867

  日期：2009.10.19

  Universal remedy: The α‐hydroxylation of β‐keto esters and a range of other suitably substituted carbonyl compounds can be effected in the presence of IBX (2‐iodoxybenzoic acid). This novel reactivity underscores the importance of IBX as a universally applicable oxidizing agent.

  通用补救措施：在IBX（2-碘氧基苯甲酸）的存在下，β-酮酯和一系列其他适当取代的羰基化合物的α-羟基化作用可以实现。这种新颖的反应性突显了IBX作为普遍适用的氧化剂的重要性。
• Oxidative Chlorination of Activated Methylene Compounds with Sodium Chloride
  作者：Stefan Kirsch、Klaus-Daniel Umland、Camilla Mayer

  DOI：10.1055/s-0033-1340793

  日期：——

  An operationally simple protocol for the direct chlorination of 1,3-dicarbonyls (and related compounds such as α-cyano ­ketones) is described. The procedure relies on mild conditions using IBX–SO 3 K as the stoichiometric oxidizing agent and the ubiquitous sodium chloride. The presence of a phase-transfer catalyst is supportive to obtain good yields in a THF–water mixture.

  描述了一种用于直接氯化 1,3-二羰基化合物（和相关化合物，如 α-氰基酮）的操作简单的协议。该过程依赖于使用 IBX-SO 3 K 作为化学计量氧化剂和无处不在的氯化钠的温和条件。相转移催化剂的存在有助于在 THF-水混合物中获得良好的产率。
• Asymmetric Transfer Hydrogenation of Functionalized Acetylenic Ketones
  作者：Zhijia Fang、Martin Wills

  DOI：10.1021/jo401284c

  日期：2013.9.6

  A systematic study of the asymmetric transfer hydrogenations of functionalized acetylenic ketones and diketones has been completed, together with a total synthesis of (S,S)-(-)-yashabushidiol B. In several cases, excellent enantioselectivities and yields were achieved.
• Diastereoselective synthesis of an advanced intermediate of the crocacin family using asymmetric transfer hydrogenation-DKR and Marshall allenylation as key reactions
  作者：Gullapalli Kumaraswamy、Vykunthapu Narayanarao、Prakash Shanigaram、Guniganti Balakishan

  DOI：10.1016/j.tet.2015.09.057

  日期：2015.11

  The natural product of a crocacin-family structural scaffold bearing consecutive anti-anti-syn stereogenic centers was accomplished by means of ATH-DKR and Marshall allenylation reactions with high stereo-control levels. The salient feature of this process is that a single catalytic asymmetric Ru-complex was used for the chirality genesis of pivotal reactions with a high substrate-to-catalyst ratio. (C) 2015 Elsevier Ltd. All rights reserved.