(Z)-Hept-3-enoic acid methyl ester

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 脂肪酰基
• 英文名称: (Z)-Hept-3-enoic acid methyl ester
• 英文别名: methyl (Z)-hept-3-enoate
• 化学式: C₈H₁₄O₂
• 分子量: 142.198
• InChiKey: MELNJTLUIHVCHX-WAYWQWQTSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.1
• 重原子数：
  10
• 可旋转键数：
  5
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.62
• 拓扑面积：
  26.3
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为产物：
  描述：

  1-三甲基硅烷-1-己炔 在 甲醇 、 六甲基磷酰三胺 、 三氟化硼乙醚 、 二异丁基氢化铝 、 lithium diisopropyl amide 作用下， 反应 23.75h， 生成 (Z)-Hept-3-enoic acid methyl ester
  参考文献：
  名称：

  (Z)-.alpha.-(trimethylsilyl) .alpha.,.beta.-unsaturated esters. Their stereoselective conversion into .alpha.,.beta.- and .beta.,.gamma.-unsaturated esters and .beta.,.gamma.-unsaturated ketene acetals

  摘要：

  Deprotonation of methyl (Z)-alpha-(trimethylsilyl) alpha,beta-unsaturated esters with lithium diisopropylamide (LDA) or with lithium hexamethyldisilazide (LHMDS) in the presence of hexamethylphosphoramide (HMPA) as an activator, followed by protonation of the intermediate dienolates with methanol, produces stereoselectively the desilylated (E)-3-alkenoic esters. Trapping the dienolates with chlorotrimethylsilane instead of methanol and then treatment of the resultant ketene acetals with aqueous hydrochloric acid affords (E)-alpha-(trimethylsilyl)-beta,gamma-alkenoic esters in 98% isomeric purities. In the absence of HMPA, (Z)-alpha-(trimethylsilyl)-alpha, beta-alkenoic esters undergo a Michael-type addition with LDA to furnish, after methanol-mediated elimination of the diisopropylamine moiety, (E)-alpha-(trimethylsilyl)-alpha,beta-alkenoic esters. In contrast to the behavior with the corresponding Z esters, deprotonation of the E esters with LDA does not require an activator. Treatment of the dienolate intermediates formed with chlorotrimethylsilane yields (O-methyl-C,O-bis(trimethylsilyl)ketene acetals, and alkylation furnishes (E)-alpha-alkyl beta,gamma-unsaturated esters. Protodesilylation of the latter compounds with tetra-n-butylammonium fluoride followed by hydrolytic workup provides trisubstituted 2-alkenoates.

  DOI：

  10.1021/jo00007a039

文献信息

• Direct C–C Bond Formation of Allylic Alcohols with CO₂ toward Carboxylic Acids by Photoredox/Nickel Dual Catalysis
  作者：Zhengning Fan、Shenhao Chen、Song Zou、Chanjuan Xi

  DOI：10.1021/acscatal.2c00418

  日期：2022.3.4

  Carboxylation of allylic alcohols with carbon dioxide is accomplished by photoredox/nickel dual catalysis, generating linear acids exclusively with good Z/E stereoselectivity. Hantzsch ester is employed as the reductant instead of stoichiometric metallic reductants, and the reaction can be conducted under room temperature with a blue LED light source. Mechanistic studies reveal that the presence of

  烯丙醇与二氧化碳的羧基化是通过光氧化还原/镍双重催化完成的，仅生成具有良好Z/E立体选择性的线性酸。采用 Hantzsch 酯代替化学计量的金属还原剂作为还原剂，反应可以在室温下用蓝色 LED 光源进行。机理研究表明，该催化体系中水的存在对反应的成功至关重要，并且反应更有可能在原位形成的烯丙基碳酸氢盐的氧化加成中进行。
• Analogs of Alpha Galactosyceramide and Uses thereof
  申请人：Cerundolo Vincenzo

  公开号：US20090239813A1

  公开（公告）日：2009-09-24

  There are disclosed compound of formula I, in which R 1 represents a hydrophobic moiety adapted to occupy the C′ channel of human CDId, R 2 represents a hydrophobic moiety adapted to occupy the A′ channel of human CDId, such that R 1 fills at least at least 30% of the occupied volume of the C′ channel compared to the volume occupied by the terminal nC 14 H 29 of the sphingosine chain of α-galactosylceramide when bound to human CDId and R 2 fills at least 30% of the occupied volume of the A′ channel compared to the volume occupied by the terminal nC 25 H 51 of the acyl chain of α-galactosylceramide when bound to human CDId R 3 represents hydrogen or OH, R a and R b each represent hydrogen and in addition, when R 3 represents hydrogen, R a and R b together may form a single bond, X represents or —CHA(CHOH) n Y or —P(═0)(0 − )0CH 2 (CH0H) m Y, in which Y represents CHB 1 B 2 , n represents an integer from 1 to 4, m represents 0 or 1, A årepresents hydrogen, one of B 1 and B 2 represents H, OH or phenyl, and the other represents hydrogen or one of B 1 and B 2 represents hydroxyl and the other represents phenyl, in addition, when n represents 4, then A together with one of B 1 and B 2 together forms a single bond and the other of B 1 and B 2 represents H, OH or OSO 3 H and pharmaceutically acceptable salts thereof; the compounds of formula I are indicted for use in the treatment of a virus, microbial infection, parasite, an autoimmune disease, cancer, allergy or asthma
• US8039670B2
  申请人：——

  公开号：US8039670B2

  公开（公告）日：2011-10-18
• (Z)-.alpha.-(trimethylsilyl) .alpha.,.beta.-unsaturated esters. Their stereoselective conversion into .alpha.,.beta.- and .beta.,.gamma.-unsaturated esters and .beta.,.gamma.-unsaturated ketene acetals
  作者：M. Ramin Najafi、Mei Ling Wang、George Zweifel

  DOI：10.1021/jo00007a039

  日期：1991.3

  Deprotonation of methyl (Z)-alpha-(trimethylsilyl) alpha,beta-unsaturated esters with lithium diisopropylamide (LDA) or with lithium hexamethyldisilazide (LHMDS) in the presence of hexamethylphosphoramide (HMPA) as an activator, followed by protonation of the intermediate dienolates with methanol, produces stereoselectively the desilylated (E)-3-alkenoic esters. Trapping the dienolates with chlorotrimethylsilane instead of methanol and then treatment of the resultant ketene acetals with aqueous hydrochloric acid affords (E)-alpha-(trimethylsilyl)-beta,gamma-alkenoic esters in 98% isomeric purities. In the absence of HMPA, (Z)-alpha-(trimethylsilyl)-alpha, beta-alkenoic esters undergo a Michael-type addition with LDA to furnish, after methanol-mediated elimination of the diisopropylamine moiety, (E)-alpha-(trimethylsilyl)-alpha,beta-alkenoic esters. In contrast to the behavior with the corresponding Z esters, deprotonation of the E esters with LDA does not require an activator. Treatment of the dienolate intermediates formed with chlorotrimethylsilane yields (O-methyl-C,O-bis(trimethylsilyl)ketene acetals, and alkylation furnishes (E)-alpha-alkyl beta,gamma-unsaturated esters. Protodesilylation of the latter compounds with tetra-n-butylammonium fluoride followed by hydrolytic workup provides trisubstituted 2-alkenoates.