(2E)-trimethyl phosphono 2-methylbut-2-enoate | 138694-30-1

• 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: (2E)-trimethyl phosphono 2-methylbut-2-enoate
• 英文别名: methyl (E)-4-bromo-2-methylbut-2-enoate；Dimethyl 3-(methoxycarbonyl)-3-methylprop-2-enylphosphonate；methyl (E)-4-dimethoxyphosphoryl-2-methylbut-2-enoate
• CAS: 138694-30-1
• 化学式: C₈H₁₅O₅P
• 分子量: 222.178
• InChiKey: VFLXXNWXGQENCF-FNORWQNLSA-N

物化性质

• 沸点：
  298.0±33.0 °C(Predicted)
• 密度：
  1.143±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  0
• 重原子数：
  14
• 可旋转键数：
  6
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.62
• 拓扑面积：
  61.8
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  (2E)-trimethyl phosphono 2-methylbut-2-enoate 在 Lindlar's catalyst 喹啉 、 lithium hydroxide 、 正丁基锂 、 ammonium cerium(IV) nitrate 、 五氯化磷 、 四丁基氟化铵 、 氢气 、 双(2-氧代-3-恶唑烷基)次磷酰氯 、 N,N-二异丙基乙胺 、 三氟乙酸 作用下， 以 四氢呋喃 、 甲醇 、 乙醇 、 二氯甲烷 、 水 、 甲苯 、 乙腈 、 苯 为溶剂， 反应 128.0h， 生成 [(2R,3S,6S,7R,8E,11S,12Z,14E)-2,5,6-三甲氧基-3,7,9,11,15-五甲基-16,20,22-三氧代-17-氮杂双环[16.3.1]二十二-1(21),8,12,14,18-五烯-10-基]氨基甲酸酯
  参考文献：
  名称：

  Asymmetric synthesis of the benzoquinoid ansamycin antitumor antibiotics: total synthesis of (+)-macbecin

  摘要：

  A convergent asymmetric synthesis of the antitumor antibiotic macbecin I has been achieved. Six of the seven stereogenic centers within the target structure were controlled using asymmetric aldol methodology, while the final stereogenic center was established through internal asymmetric induction. Fragment coupling was accomplished using a mild, titanium tetrachloride mediated aldol reaction. The C1-C5 unsaturated dienic ester was stereoselectively incorporated through a kinetically controlled Horner-Emmons olefination. Macrolactamization and subsequent refunctionalization afforded macbecin I.

  DOI：

  10.1021/jo00054a035
• 作为产物：
  描述：

  methyl (E)-4-bromo-2-methylbut-2-enoate 、 三甲氧基磷 反应 1.0h， 以73%的产率得到(2E)-trimethyl phosphono 2-methylbut-2-enoate
  参考文献：
  名称：

  Asymmetric synthesis of the benzoquinoid ansamycin antitumor antibiotics: total synthesis of (+)-macbecin

  摘要：

  A convergent asymmetric synthesis of the antitumor antibiotic macbecin I has been achieved. Six of the seven stereogenic centers within the target structure were controlled using asymmetric aldol methodology, while the final stereogenic center was established through internal asymmetric induction. Fragment coupling was accomplished using a mild, titanium tetrachloride mediated aldol reaction. The C1-C5 unsaturated dienic ester was stereoselectively incorporated through a kinetically controlled Horner-Emmons olefination. Macrolactamization and subsequent refunctionalization afforded macbecin I.

  DOI：

  10.1021/jo00054a035

文献信息

• Theoretical and Experimental Determination of the Effects Governing the Transannular Diels−Alder Reaction of Trans−Trans−Cis Systems with or without Activation of the Dienophile
  作者：Samuel Fortin、Louis Barriault、Yves L. Dory、Pierre Deslongchamps

  DOI：10.1021/ja0109491

  日期：2001.8.1

  A thorough study of the transannular Diels-Alder (TADA) reaction of trans-trans-cis macrocyclic trienes was carried out. It led to a better understanding of various parameters that govern the TADA reaction in particular and the Diels-Alder reaction in general. Thus, carbonyl activation of the dienophile and substitution of the diene are discussed, as well as the presence of substituents on the macrocycle

  对反-反-顺大环三烯的跨环狄尔斯-阿尔德（TADA）反应进行了深入研究。它有助于更​​好地了解控制 TADA 反应的各种参数，以及一般的 Diels-Alder 反应。因此，讨论了亲二烯体的羰基活化和二烯的取代，以及大环上取代基的存在及其在过渡态水平上的各自影响。
• Total Synthesis of (−)-Nodulisporic Acids D, C, and B: Evolution of a Unified Synthetic Strategy
  作者：Yike Zou、Xiangqin Li、Yun Yang、Simon Berritt、Jason Melvin、Stephen Gonzales、Matthew Spafford、Amos B. Smith

  DOI：10.1021/jacs.8b04053

  日期：2018.8.1

  A unified synthetic strategy leading to the total synthesis of (-)-nodulisporic acids D, C, and B is described. Key synthetic transformations include a nickel-chromium-mediated cyclization, an aromatic ring functionalization employing a novel copper-promoted alkylation, a palladium-catalyzed cross-coupling cascade/indole ring construction, and a palladium-mediated regio- and diastereoselective allylic

  描述了导致 (-)-球孢酸 D、C 和 B 全合成的统一合成策略。关键的合成转化包括镍铬介导的环化、采用新型铜促进的烷基化的芳环官能化、钯催化的交叉偶联级联/吲哚环结构以及钯介导的区域和非对映选择性烯丙基取代/环化反应，后者构建环D。
• Total Synthesis of (−)-Nodulisporic Acid D
  作者：Yike Zou、Jason E. Melvin、Stephen S. Gonzales、Matthew J. Spafford、Amos B. Smith

  DOI：10.1021/jacs.5b04728

  日期：2015.6.10

  A convergent total synthesis of the architecturally complex indole diterpenoid (-)-nodulisporic acid D has been achieved. Key synthetic transformations include vicinal difunctionalization of an advanced α,β-unsaturated aldehyde to form the E,F-trans-fused 5,6-ring system of the eastern hemisphere and a cascade cross-coupling/indolization protocol leading to the CDE multisubstituted indole core.

  结构复杂的吲哚二萜 (-)-nodulisporic 酸 D 的收敛全合成已经实现。关键的合成转化包括先进的 α,β-不饱和醛的邻位双官能化以形成东半球的 E,F-反式融合 5,6-环系统和导致 CDE 多取代吲哚的级联交叉偶联/吲哚化方案核。
• Total Syntheses of Furaquinocin A, B, and E
  作者：Barry M. Trost、Oliver R. Thiel、Hon-Chung Tsui

  DOI：10.1021/ja0364118

  日期：2003.10.1

  A modular approach to the total synthesis of furaquinocins culminated in the total syntheses of furaquinocin A, B, and E. A Pd-catalyzed dynamic kinetic asymmetric transformation (DYKAT) on carbonates derived from Baylis-Hillman adducts, followed by a reductive Heck cyclization allows the enantio- and diastereoselective construction of dihydrobenzofuran 32. Introduction of a double unsatured side chain

  使用交叉复分解或闭环复分解可以实现侧链的立体选择性延伸。获得的后期中间体成功转化为呋喃喹啉A和B。
• Enantioselective synthesis of the top half of tetronolide
  作者：William R. Roush、Kazuo Koyama

  DOI：10.1016/s0040-4039(00)60939-5

  日期：1992.10

  A highly enantio- and diastereoselective synthesis of the top half spirotetronate subunit (3) of tetronolide is described.

  描述了对四氢萜内酯的上半螺形亚油酸酯亚基（3）的高度对映体和非对映体选择性合成。