diethyl-2-(cyclohexylimino)vinyl phosphonate | 54364-57-7

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 有机膦酸及其衍生物
• 英文名称: diethyl-2-(cyclohexylimino)vinyl phosphonate
• 英文别名: <2-(Cyclohexylimino)ethyl>phosphonic acid diethyl ester；Nagata's reagent；2-Cyclohexylimino-ethanphosphonsaeure-diethylester；(EtO)2P(O)CH2CHNc-Hex；(EtO)2P(O)CH2CH=NCy；N-cyclohexyl-2-diethoxyphosphorylethanimine
• CAS: 54364-57-7
• 化学式: C₁₂H₂₄NO₃P
• 分子量: 261.301
• InChiKey: MSAXEVSZBONZIC-UHFFFAOYSA-N

物化性质

• 沸点：
  371.1±34.0 °C(Predicted)
• 密度：
  1.13±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.6
• 重原子数：
  17
• 可旋转键数：
  7
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.92
• 拓扑面积：
  47.9
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  (1S,3R)-8-formyl-3,7-dimethyl-1,2,3,4-tetrahydronaphthalen-1-yl acetate 、 diethyl-2-(cyclohexylimino)vinyl phosphonate 在 双(三甲基硅烷基)氨基钾 作用下， 以 四氢呋喃 、 甲苯 为溶剂， 反应 4.25h， 以88%的产率得到(1S,3R)-3,7-dimethyl-8-((E)-3-oxoprop-1-enyl)-1,2,3,4-tetrahydronaphthalen-1-yl acetate
  参考文献：
  名称：

  HMG-CoA还原酶抑制剂FR901512和FR901516的结构阐明和对映选择性全合成

  摘要：

  审查了有效的HMG-CoA还原酶抑制剂FR901512（1）和FR901516（2）的对映选择性全合成。FR901512分15步由市售化合物通过2步制备，总收率16.3％（平均收率89％）。这项研究验证了我们开发的催化不对称Nozaki-Hiyama反应的适用性和可靠性。这些反应使得这些新的他汀类药物能够进行简明，有效和无保护基的对映选择性总合成。 不对称催化-对映选择性合成-野崎aki山反应-结构解析-全合成

  DOI：

  10.1055/s-0029-1216980

文献信息

• Structure Elucidation and Enantioselective Total Synthesis of the Potent HMG-CoA Reductase Inhibitor FR901512 via Catalytic Asymmetric Nozaki−Hiyama Reactions
  作者：Masahiro Inoue、Masahisa Nakada

  DOI：10.1021/ja070812w

  日期：2007.4.1

  The structure elucidation and enantioselective total synthesis of the potent HMG-CoA reductase inhibitor FR901512 were accomplished. FR901512 was prepared in 15 steps from the commercially available 2-bromo-4-methylbenzaldehyde via FR901516 in 16.3% overall yield (89% average yield). The catalytic asymmetric Nozaki−Hiyama reactions developed by us proved their applicability and reliability through

  完成了强效HMG-CoA还原酶抑制剂FR901512的结构解析和对映选择性全合成。FR901512 由市售的 2-溴-4-甲基苯甲醛通过 FR901516 分 15 个步骤制备，总产率为 16.3%（平均产率为 89%）。我们开发的催化不对称 Nozaki-Hiyama 反应通过这项工作证明了它们的适用性和可靠性，从而实现了这些新他汀类药物的简洁、高效和无保护基团的对映选择性全合成。
• Intra- and intermolecular hetero-Diels-Alder reactions. 45. Simple and induced diastereoselectivity in intramolecular hetero-Diels-Alder reactions of 1-oxa-1,3-butadienes. Experimental data and calculations
  作者：Lutz F. Tietze、Holger Geissler、Jens Fennen、Thomas Brumby、Siegbert Brand、Gerhard Schulz

  DOI：10.1021/jo00080a030

  日期：1994.1

  The simple and induced diastereoselectivity of the intramolecular hetero-Diels-Alder reaction of the alkylidene 1,3-dicarbonyl compounds 7a-e, obtained in situ by Knoevenagel condensation of the aldehydes 5a-e and dimethylbarbituric acid 6, was investigated experimentally and theoretically. In all examples the selectivity is very high; thus the domino reaction of 5a and 6 gives nearly exclusively the trans-fused tricyclic dihydropyran 8 (trans/cis = 98.8:1.2). In the similar reactions of the chiral aldehydes 5b-e and 6 the trans-cycloadducts 28, 33, 36, and 41 are the main products out of four possible diastereomers. The induced diastereoselectivity for the reaction of 5b and 5e with 6 is >99:1 and for the reaction of 5e and Sd-with 6, 95.2:3.6 and 94.1:4.7, respectively. Semiempirical AM1 calculations have been used to locate the transition structures of the intramolecular hetero-Diels-Alder reaction of 7a. The results were employed to create new parameters for the MM2-type force-field to determine the transition structures of 7b-e. The obtained data were compared with the experimental results of the cycloadditions and showed an excellent agreement.
• Synthesis from pregnenolone of fluorescent cholesterol analog probes with conjugated unsaturation in the side chain
  作者：Jacinta Drew、Marie Letellier、Peter Morand、Arthur G. Szabo

  DOI：10.1021/jo00227a020

  日期：1987.9
• Synthetic studies on (+)-bucidarasin C: two diastereoselective transannular reactions producing cis-decaline derivatives that show reversal selectivity
  作者：Akinobu Nakahara、Misaki Kanbe、Masahisa Nakada

  DOI：10.1016/j.tetlet.2012.01.058

  日期：2012.3

  This manuscript describes studies on the construction of the cis-decaline core of (+)-bucidarasin C. The transannular Diels-Alder (TADA) reaction of a macrocyclic lactone successfully afforded the desired cis-decaline derivative in a stereoselective manner. On the other hand, the stereoselective transannular cascade Michael (TACM) reaction of the parent macrocyclic lactone afforded the diastereomeric cis-decaline derivative as the major product. (C) 2012 Elsevier Ltd. All rights reserved.
• Structure Elucidation and Enantioselective Total Synthesis of the HMG-CoA Reductase Inhibitors FR901512 and FR901516
  作者：Masahisa Nakada、Masahiro Inoue

  DOI：10.1055/s-0029-1216980

  日期：2009.11

  overall yield (89% average yield). This study validated the applicability and reliability of the catalytic asymmetric Nozaki-Hiyama reactions that were developed by us. These reactions enabled the concise, efficient, and protecting-group-free enantioselective total syntheses of these new statins. asymmetric catalysis - enantioselective synthesis - Nozaki-Hiyama reaction - structure elucidation - total

  审查了有效的HMG-CoA还原酶抑制剂FR901512（1）和FR901516（2）的对映选择性全合成。FR901512分15步由市售化合物通过2步制备，总收率16.3％（平均收率89％）。这项研究验证了我们开发的催化不对称Nozaki-Hiyama反应的适用性和可靠性。这些反应使得这些新的他汀类药物能够进行简明，有效和无保护基的对映选择性总合成。 不对称催化-对映选择性合成-野崎aki山反应-结构解析-全合成