methyl (Z)-2-((4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)methyl)but-2-enoate | 929111-04-6

• 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: methyl (Z)-2-((4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)methyl)but-2-enoate
• 英文别名: methyl (Z)-2-[(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)methyl]acrylate；trans-MeCHCCOOMe(CH2B(OCMe2)2)；Methyl (2Z)-2-[(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)methyl]but-2-enoate；methyl (Z)-2-[(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)methyl]but-2-enoate
• CAS: 929111-04-6
• 化学式: C₁₂H₂₁BO₄
• 分子量: 240.107
• InChiKey: ZVFWEBACPDQANI-CLFYSBASSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.2
• 重原子数：
  17
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.75
• 拓扑面积：
  44.8
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  环己烷基甲醛 、 methyl (Z)-2-((4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)methyl)but-2-enoate 在 In(OSO₂CF₃)3 作用下， 以 甲苯 为溶剂， 反应 30.0h， 以90%的产率得到(Z)-5-cyclohexyl-3-ethylidenedihydrofuran-2(3H)-one
  参考文献：
  名称：

  Acidity-Directed Synthesis of Substituted γ-Butyrolactones from Aliphatic Aldehydes

  摘要：

  The strength of the Lewis or Bronsted acids controls the formation of either beta,gamma-disubstituted-alpha-methylene-gamma-butyrolactones or gamma-substituted-alpha-alkylidene-gamma-butyrolactones via the lactonization or oxonia cope rearrangement-lactonization, respectively, of the borate intermediates resulting from the crotylboration of aliphatic aldehydes with ester-containing crotylboronates, such as (E)-methyl 2-boramethyl-2-butenoates.

  DOI：

  10.1021/ol0705806
• 作为产物：
  描述：

  2-(氯甲基)-4,4,5,5-四甲基-1,3,2-二噁硼烷 、 2-丁炔酸甲酯 在 二异丁基氢化铝 六甲基磷酰三胺 、 copper(l) iodide 、 甲基锂 作用下， 以 四氢呋喃 、 乙醚 、 甲苯 为溶剂， 反应 5.0h， 生成 methyl (2E)-2-[(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)methyl]-but-2-enoate 、 methyl (Z)-2-((4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)methyl)but-2-enoate
  参考文献：
  名称：

  β-官能化的烯丙基硼酸酯的对映选择性加成到醛和醛亚胺上。立体控制合成α-亚甲基-γ-内酯和内酰胺

  摘要：

  我们报告有关手性β-烷氧基羰基烯丙基硼酸酯在醛和亚胺上的缩合反应的发展结果。这些烯丙基硼酸酯以高度对映选择性和非对映特异性的方式添加，以提供生物学上和合成上有用的手性α-亚甲基-γ-丁内酯和内酰胺。亲电子试剂的性质（醛对亚胺）显示出对反应机理的巨大影响，可能通过不同的过渡态指导了过程的立体选择性。

  DOI：

  10.1016/j.tet.2007.12.046

文献信息

• Novel Isomerically Pure Tetrasubstituted Allylboronates:  Stereocontrolled Synthesis of α-Exomethylene γ-Lactones as Aldol-Like Adducts with a Stereogenic Quaternary Carbon Center
  作者：Jason W. J. Kennedy、Dennis G. Hall

  DOI：10.1021/ja016391e

  日期：2002.2.1

  1-alkoxycarbonyl vinylcopper(I) intermediates from the conjugate addition of organocuprates onto acetylenic esters were trapped with very high cis-addition selectivity with iodomethylboronic esters in the presence of HMPA. The resulting isomerically pure 3,3-disubstituted allylboronates react with aldehydes in a highly diastereo- and enantioselective manner, providing α-exomethylene γ-lactones with a stereogenic

  尽管它们固有的异构化倾向和低反应性，1-烷氧基羰基乙烯基铜 (I) 中间体在 HMPA 存在下与碘甲基硼酸酯以非常高的顺式加成选择性捕获了有机铜酸盐与炔酸酯的共轭加成。所得的异构纯 3,3-二取代烯丙基硼酸酯以高度非对映选择性和对映选择性方式与醛反应，提供具有立体异构四元 β-碳中心的 α-外亚甲基 γ-内酯。
• Total Synthesis of the Eupomatilones
  作者：Soumya Mitra、Srinivas Reddy Gurrala、Robert S. Coleman

  DOI：10.1021/jo701415m

  日期：2007.11.1

  Full details of the total syntheses of five members of the eupomatilone family of lignans are reported.
• Imine allylation using 2-alkoxycarbonyl allylboronates as an expedient three-component reaction to polysubstituted α-exo-methylene-γ-lactams
  作者：Tim G. Elford、Dennis G. Hall

  DOI：10.1016/j.tetlet.2008.09.112

  日期：2008.12

  alpha-exo-Methylene-gamma-lactams are key structural units in a wide variety of biologically active natural products. A concise route to the formation of polysubstituted alpha-exo-methylene-gamma-lactams is described. In this three-component reaction, an imine is formed from an aldehyde and ammonia in situ, and is subsequently allylated through the use of a 2-alkoxycarbonyl allylboronate. Due to the ester functionality, the addition intermediate subsequently undergoes in situ cyclization to form the observed alpha-exo-methylene-gamma-lactam products. This route allows access to highly substituted alpha-exo-methylene-gamma-lactams in moderate to excellent yields. (C) 2008 Elsevier Ltd. All rights reserved.