methyl 4-oxo-6-(trimethylsilyl)hex-5-ynoate | 88761-59-5

• 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: methyl 4-oxo-6-(trimethylsilyl)hex-5-ynoate
• 英文别名: methyl 4-oxo-6-(trimethylsilyl)-5-hexynoate；5-Hexynoic acid, 4-oxo-6-(trimethylsilyl)-, methyl ester；methyl 4-oxo-6-trimethylsilylhex-5-ynoate
• CAS: 88761-59-5
• 化学式: C₁₀H₁₆O₃Si
• 分子量: 212.321
• InChiKey: FORPZPRMQFFKAV-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.39
• 重原子数：
  14
• 可旋转键数：
  5
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.6
• 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：

  methyl 4-oxo-6-(trimethylsilyl)hex-5-ynoate 在 吡啶 、 4-二甲氨基吡啶 、 sodium tetrahydroborate 、 氨 、 copper(l) chloride 作用下， 以 1,4-二氧六环 、 甲醇 、 溶剂黄146 为溶剂， 反应 116.0h， 生成 1-methyl-5-(3-pyrrolidino-1-propynyl)-2-pyrrolidone
  参考文献：
  名称：

  Conformationally restricted analogs of the muscarinic agent N-methyl-N-(1-methyl-4-pyrrolidino-2-butynyl)acetamide

  摘要：

  Conformationally restricted analogues of the selective partial muscarinic agonist N-methyl-N-(1-methyl-4-pyrrolidino-2-butynyl)acetamide (BM 5; 2) were synthesized. The compounds were tested for muscarinic and antimuscarinic activity in the isolated guinea pig ileum and in intact mice. They were found to be moderately potent muscarinic antagonists or weak partial agonists. The new compounds were less potent than 2 in inhibiting (-)-[3H]-N-methylscopolamine binding in the rate cerebral cortex. Thus, structural modifications of 2 in which part of the amide moiety has been connected with the methyl group in the butynyl chain to form a five-membered ring decrease affinity and in most cases abolish efficacy.

  DOI：

  10.1021/jm00124a022
• 作为产物：
  描述：

  6-trimethylsilylhex-5-ynoic acid methyl ester 在 dirhodium(II) tetrakis(caprolactam) 叔丁基过氧化氢 作用下， 以 水 为溶剂， 反应 30.0h， 以79%的产率得到methyl 4-oxo-6-(trimethylsilyl)hex-5-ynoate
  参考文献：
  名称：

  己内酯二甲酸在水中催化的炔丙基氧化：有效获得α，β-乙炔酮

  摘要：

  己酸内酯（II）（1，Rh 2（cap）4）与70％w / w叔丁基过氧化氢水溶液（T-HYDRO）是一种高效的催化氧化方案，用于将炔烃进行CH选择性氧化成炔丙基酮。在温和条件下，使用廉价且易于处理的氧化剂，很容易在水性溶剂中发生氧化。以高达80％的分离产率生成α，β-乙炔羰基化合物。

  DOI：

  10.1021/jo800382p

文献信息

• Synthesis of the C13–C29 fragment of leiodolide A: allylic asymmetric induction on the stereochemical course of iodolactonization
  作者：Jihoon Lee、James S. Panek

  DOI：10.1016/j.tetlet.2015.10.087

  日期：2015.12

  selective Stille cross-coupling was employed to assemble the (Z,E)-diene bearing the C15 allylic alcohol, which was followed by iodolactonization to introduce C16–C17 vicinal stereocenters. The stereochemical course of iodolactonization that is based on the solid mechanistic underpinnings arising from allylic asymmetric induction is also discussed.

  描述了莱奥多利德A C13–C29片段的立体控制合成。该天然产物是从深海海洋海绵皮癣菌中分离出来的。高度选择性的斯蒂勒交叉偶联用于组装带有C15烯丙基醇的（Z，E）-二烯，然后进行碘内酯化，引入C16-C17邻位立体中心。还讨论了基于烯丙基不对称诱导产生的固体机制基础的碘伏内酯化的立体化学过程。
• [EN] FATTY ACID DERIVATIVES AND THEIR USE<br/>[FR] DÉRIVÉS D'ACIDES GRAS ET UTILISATION ASSOCIÉE
  申请人：US HEALTH

  公开号：WO2019010414A1

  公开（公告）日：2019-01-10

  This disclosure concerns fatty acid derivatives, pharmaceutical compositions comprising the fatty acid derivatives, and methods of using the fatty acid derivatives, for example, to treat inflammation, chronic itch, chronic pain, an autoimmune disorder, atherosclerosis, a skin disorder, arthritis, a neurodegenerative disorder, or a psychiatric disorder in a subject. In some embodiments, the fatty acid derivative is a compound, or a stereoisomer, tautomer, or pharmaceutically acceptable salt thereof, having a structure according to: (I) wherein X is from 1-16 carbons in length, Z is aliphatic from 1-16 carbons in length, or is not present, Y is selected from: (II) R1, R2, and R3 are independently hydrogen or lower alkyl, R4 is lower alkyl, hydroxyl, carboxyl, or amine, R5 is hydrogen, lower alkyl, or halide, R6 is hydroxyl or substituted thiol, and each R7 is independently hydrogen or fluoride or is not present and the adjacent carbons form alkyne.

  这份披露涉及脂肪酸衍生物，包括含有脂肪酸衍生物的药物组合物，以及使用脂肪酸衍生物的方法，例如用于治疗炎症、慢性瘙痒、慢性疼痛、自身免疫性疾病、动脉粥样硬化、皮肤疾病、关节炎、神经退行性疾病或精神疾病的主体。在某些实施例中，脂肪酸衍生物是一种化合物，或其立体异构体、互变异构体或药用可接受的盐，其结构如下：(I)其中X的长度为1-16个碳，Z是1-16个碳的脂肪族，或者不存在，Y选自：(II)R1、R2和R3独立地是氢或较低的烷基，R4是较低的烷基、羟基、羧基或胺基，R5是氢、较低的烷基或卤素，R6是羟基或取代硫醇，每个R7独立地是氢或氟或不存在，相邻的碳形成炔烃。
• Copper-Catalyzed Synthesis of γ-Amino Acids Featuring Quaternary Stereocenters
  作者：José Enrique Gómez、Wusheng Guo、Silvia Gaspa、Arjan W. Kleij

  DOI：10.1002/anie.201709511

  日期：2017.11.20

  Open sesame: The first general asymmetric synthesis of γ,γ-disubstituted γ-amino acids by copper-catalyzed ring opening of nonstrained lactones with amines is reported. This catalytic system allows the synthesis of a series of highly functionalized γ-amino acids, featuring quaternary stereocenters, with excellent enantiomeric ratios of up to 98:2 and yields of up to 98 %.

  开孔芝麻：报道了通过铜催化非应变内酯与胺的开环反应，首次普遍不对称合成γ，γ-二取代的γ-氨基酸。该催化系统可以合成具有季立体中心的一系列高度官能化的γ-氨基酸，对映体比率高达98：2，产率高达98％。
• Asymmetric reductions of propargyl ketones
  作者：M. Mark midland、Alfonso tramontano、Aleksander kazubski、Richard S. graham、David J.S. tsai、Daniel B. cardin

  DOI：10.1016/s0040-4020(01)82422-4

  日期：1984.1

  Propargyl ketones are readily reduced by the asymmetric reducing agent B-3-pinanyl-9- borabicyclo[3.3.1]-nonane (Alpine-borane). The reagent prepared from (+)-α-pinene and 9-BBN provides the R enantiomer while the S enantiomer can be obtained from (-)-α-pinene. Alternatively the S enantiomer can be prepared from the reagent derived from 9-BBN and the benzyl ether of nopol (6,6-dimethyl-bicyclo[3.11

  炔丙基酮很容易被不对称还原剂B -3-pinanyl-9- borabicyclo [3.3.1]-壬烷（Alpine-borane）还原。由（+）-α-pine烯和9-BBN制备的试剂可提供R对映体，而S对映异构体可获自（-）-α-obtained烯。或者，S对映异构体可以由衍生自9-BBN和nopol的苄基醚（6，6-二甲基-双环[3.11。]庚-2-烯-2-乙醇）的试剂制备。获得高对映体诱导的限制因素通常是α--烯的对映体纯度。用100％对映体纯的α-pine烯，可获得基本上100％ee的炔丙醇。提出了导致这种显着选择的过渡态的预测合理化。炔丙醇的乙炔单元为转化为其他有用的旋光产物提供了方便的方法。说明了炔丙醇在合成光学活性的α-和β-取代的γ-内酯以及δ-内酯中的用途。
• Asymmetric reduction of ethynyl ketones and ethynylketoesters by secondary alcohol dehydrogenase from Thermoanaerobacter ethanolicus †
  作者：Christian Heiss、Robert S. Phillips

  DOI：10.1039/b001329n

  日期：——

  Secondary alcohol dehydrogenase (SADH) from Thermoanaerobacter ethanolicus, an NADP-dependent, thermostable oxidoreductase, reduces ethynyl ketones and ethynylketoesters enantioselectively to the corresponding propargyl (propargyl = prop-2-ynyl) alcohols. Ethynyl ketones, in general, are reduced with moderate enantioselectivity (with the exception of 4-methylpent-1-yn-3-one, which gives the (S)-alcohol

  仲醇脱氢酶（SADH）从嗜热ethanolicus，一个北美发展计划依赖性的热稳定氧化还原酶将乙炔基酮和乙炔基酮酸酯对映选择性地还原为相应的炔丙基（炔丙基=炔-2-炔基） 酒类。乙炔基酮类通常以中等对映选择性降低（除 4-甲基戊-1-yn-3-一，得到（S）醇的ee> 98％）。虽然乙炔基酮类带有少量（最多正丙基）烷基取代基还原为（S）醇，较大的乙炔基酮类给出（R）-醇。相反，乙炔基酮酸酯被转化为具有优异光学纯度的（R）-乙炔基羟基酯。出乎意料的是，与乙炔基羟基酯相比，异丙基乙炔基酮酯具有更高的化学收率和更高的对映选择性。甲基或乙基乙炔基酮酸酯。光学纯的乙炔基羟基酯可用作不对称合成的有用的手性结构单元。