dimethyl 2-(furan-3-ylmethylene)malonate | 909904-14-9

• 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: dimethyl 2-(furan-3-ylmethylene)malonate
• 英文别名: Dimethyl 2-(furan-3-ylmethylidene)propanedioate；dimethyl 2-(furan-3-ylmethylidene)propanedioate
• CAS: 909904-14-9
• 化学式: C₁₀H₁₀O₅
• 分子量: 210.186
• InChiKey: RLYACLJZJDHXTH-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.3
• 重原子数：
  15
• 可旋转键数：
  5
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.2
• 拓扑面积：
  65.7
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  dimethyl 2-(furan-3-ylmethylene)malonate 在 sodium tetrahydroborate 、 lithium aluminium tetrahydride 、 正丁基锂 、 cyclopentadienylruthenium(II) trisacetonitrile hexafluorophosphate 、 (R)-6-(2-chloronaphthalen-1-yl)-5-methylpyridine-2-carboxylic acid 、 4-甲基苯磺酸吡啶 、 sodium hydride 作用下， 以 四氢呋喃 、 甲醇 、 正己烷 、 二氯甲烷 、 N,N-二甲基乙酰胺 为溶剂， 反应 54.25h， 生成 2',2'-dimethyl-7-vinyl-6,7-dihydro-4H-spiro[benzofuran-5,5'-[1,3]dioxane]
  参考文献：
  名称：

  钌催化五元硫属杂芳烃的不对称脱水烯丙基环化

  摘要：

  呋喃和噻吩的不对称脱水分子内烯丙基化反应使用手性吡啶羧酸（即 Cl-Naph-PyCOOH）的阳离子环戊二烯基-钌 (CpRu) 络合物进行。呋喃和噻吩与烯丙醇相连，使用 0.1-5 mol% 的催化剂以高产率和对映选择性得到相应的双环化合物。发现该反应通过与我们小组先前报道的类似的对映面选择机制进行，除了生成中间体 σ-烯丙基复合物外，还涉及卤素和氢键的形成。

  DOI：

  10.1055/a-1523-6826
• 作为产物：
  描述：

  3-糠醛 、 丙二酸二甲酯 在 哌啶 、 溶剂黄146 作用下， 以 甲苯 为溶剂， 反应 3.0h， 以84%的产率得到dimethyl 2-(furan-3-ylmethylene)malonate
  参考文献：
  名称：

  Tetrahydro-1,3-oxazepines via Intramolecular Amination of Cyclopropylmethyl Cation

  摘要：

  An efficient synthesis of tetrahydro-1,3-oxazepines was developed involving the regioselective intramolecular amination of cyclopropylmethyl cation. The cation was generated by the abstraction of one imidate group in bis-imidate bearing a carbocation-stabilizing substituent. Using 1,1,2,3-tetrasubstituted cyclopropane substrates, highly diastereoselective intramolecular amination to trans-tetrahydro-1,3-oxazepines was achieved. The resulting tetrahydro-1,3-oxazepines were transformed to the homoallylamine derivatives in high yields.

  DOI：

  10.1021/acs.orglett.5b01014

文献信息

• A N,N′-dioxide/Mg(OTf)₂ complex catalyzed enantioselective α-addition of isocyanides to alkylidene malonates
  作者：Weiwei Luo、Xiao Yuan、Lili Lin、Pengfei Zhou、Xiaohua Liu、Xiaoming Feng

  DOI：10.1039/c6sc00689b

  日期：——

  A simple and efficient catalytic asymmetric [small alpha]-addition of isocyanides to alkylidene malonates was realized using a chiral N,N[prime or minute]-dioxide/MgII catalyst. A variety of 2-alkyl-5-aminoxazoles were obtained in up to 99% yield and 96% ee, and could be converted to imides and dipeptides.

  使用手性N，N [伯或分钟]二氧化物/ Mg II催化剂，可以实现简单有效的异氰酸酯向亚烷基丙二酸酯的催化不对称α-小加成反应。以高达99％的收率和96％的ee获得了各种2-烷基-5-氨基恶唑，并且可以将其转化为酰亚胺和二肽。
• One-Pot Synthesis of Multisubstituted Butyrolactonimidates: Total Synthesis of (−)-Nephrosteranic Acid
  作者：Huijing Wang、Pei Tang、Qilong Zhou、Dan Zhang、Zhitao Chen、Hongxiu Huang、Yong Qin

  DOI：10.1021/jo5029166

  日期：2015.3.6

  one-pot, three-step cascade reaction in which (R)-N-tert-butanesulfinyl imidates and α,β-unsaturated diesters undergo highly stereoselective Michael addition, anion-oxidative hydroxylation, and cyclization. The synthesized butyrolactonimidates are versatile intermediates for preparation of substituted butyrolactones and furans. The usefulness of this cascade reaction is demonstrated through the concise

  多取代的手性butyrolactonimidates已经通过一釜，三步级联反应合成，其中（- [R ）- ñ -叔-butanesulfinyl亚氨酸酯和α，β -不饱和二酯经历高度立体选择性迈克尔加成，阴离子氧化羟基化，环化和。合成的丁内酯酰胺酸盐是用于制备取代的丁内酯和呋喃的通用中间体。该级联反应的有用性通过天然产物（-）-肾上腺酸的简明全合成得到了证明。
• Generation of <i>N</i>-Acyliminium Ions via Intramolecular Conjugate Addition Reactions:  A Strategy for the Total Synthesis of Nakadomarin A
  作者：Mark G. Nilson、Raymond L. Funk

  DOI：10.1021/ol061463y

  日期：2006.8.1

  [reaction: see text] The rapid construction of the tetracyclic core ring system of nakadomarin A via a tandem enecarbamate Michael addition/N-acyliminium ion cyclization is described.

  [反应：见正文]描述了通过串联烯氨基甲酸酯迈克尔加成/ N-酰亚胺离子环化反应快速构建的那卡多马林A四环核环系统。
• Tetrahydro-1,3-oxazepines via Intramolecular Amination of Cyclopropylmethyl Cation
  作者：Marija Skvorcova、Liene Grigorjeva、Aigars Jirgensons

  DOI：10.1021/acs.orglett.5b01014

  日期：2015.6.19

  An efficient synthesis of tetrahydro-1,3-oxazepines was developed involving the regioselective intramolecular amination of cyclopropylmethyl cation. The cation was generated by the abstraction of one imidate group in bis-imidate bearing a carbocation-stabilizing substituent. Using 1,1,2,3-tetrasubstituted cyclopropane substrates, highly diastereoselective intramolecular amination to trans-tetrahydro-1,3-oxazepines was achieved. The resulting tetrahydro-1,3-oxazepines were transformed to the homoallylamine derivatives in high yields.
• Ruthenium-Catalyzed Asymmetric Dehydrative Allylic Cyclization of Five-Membered Chalcogen Heteroaromatics
  作者：Shinji Tanaka、Masato Kitamura、Shoutaro Iwase、Sena Kanda、Marie Kato、Yutaro Kiriyama

  DOI：10.1055/a-1523-6826

  日期：2021.9

  intramolecular allylation reactions of furan and thiophene were performed using a cationic cyclopentadienyl-ruthenium (CpRu) complex of a chiral pyridine carboxylic acid, namely Cl-Naph-PyCOOH. Both furan and thiophene tethered with an allylic alcohol gave the corresponding bicyclic compounds in high yields and enantioselectivities using 0.1–5 mol% of the catalyst. The reaction was found to proceed via

  呋喃和噻吩的不对称脱水分子内烯丙基化反应使用手性吡啶羧酸（即 Cl-Naph-PyCOOH）的阳离子环戊二烯基-钌 (CpRu) 络合物进行。呋喃和噻吩与烯丙醇相连，使用 0.1-5 mol% 的催化剂以高产率和对映选择性得到相应的双环化合物。发现该反应通过与我们小组先前报道的类似的对映面选择机制进行，除了生成中间体 σ-烯丙基复合物外，还涉及卤素和氢键的形成。