Ethyl (4R)-4-<(4R)-2,2-diethyl-1,3-dioxolan-4-yl>-2-methyl-2-pentenoate | 153185-64-9

• 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: Ethyl (4R)-4-<(4R)-2,2-diethyl-1,3-dioxolan-4-yl>-2-methyl-2-pentenoate
• 英文别名: ethyl (E,4R)-4-[(4R)-2,2-diethyl-1,3-dioxolan-4-yl]-2-methylpent-2-enoate
• CAS: 153185-64-9
• 化学式: C₁₅H₂₆O₄
• 分子量: 270.369
• InChiKey: IOSFCBJFAHDJTI-YURTZEIPSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.2
• 重原子数：
  19
• 可旋转键数：
  7
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.8
• 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：

  Ethyl (4R)-4-<(4R)-2,2-diethyl-1,3-dioxolan-4-yl>-2-methyl-2-pentenoate 在 盐酸 、 三甲基铝 、 二甲羟胺盐酸盐 、 三乙胺 作用下， 以 四氢呋喃 、 二氯甲烷 、 水 为溶剂， 反应 48.5h， 生成 (E,5R,6R)-6,7-bis[[tert-butyl(dimethyl)silyl]oxy]-3,5-dimethylhept-3-en-2-one
  参考文献：
  名称：

  具有天然构型的calyculins四烯片段的合成

  摘要：

  四烯片段的合成2中，C 1 -C 12部分，calyculins（的1 f）曾通过使用的Stille的乙烯基碘的（C联接完成6 -C 12）单元4与腈（C 1 - C 5）单元3，然后按照巴顿法将其转化为碘乙烯官能团。

  DOI：

  10.1016/0040-4039(93)88104-q
• 作为产物：
  描述：

  diethyl (2S,3R)-2-methylmalate 在 草酰氯 、 dimethyl sulfide borane 、 对甲苯磺酸 、 二甲基亚砜 、 N,N-二异丙基乙胺 作用下， 以 四氢呋喃 、 二氯甲烷 、 N,N-二甲基甲酰胺 为溶剂， 反应 23.25h， 生成 Ethyl (4R)-4-<(4R)-2,2-diethyl-1,3-dioxolan-4-yl>-2-methyl-2-pentenoate
  参考文献：
  名称：

  Stereoselective Hydrogen Transfer Reactions Involving Acyclic Radicals. Tandem Substituted Tetrahydrofuran Formation and Stereoselective Reduction: Synthesis of the C17-C22 Subunit of Ionomycin

  摘要：

  The tandem iodoetherification reaction and stereoselective reduction of acyclic radicals has been used in the stereocontrolled synthesis of substituted tetrahydrofurans. Such a tetrahydrofuran intermediate is regioselectively cleaved using Me(2)BBr to reveal the acyclic array 2 which represents the C-17-C-22 subunit of ionomycin. In experiments that provide for a better understanding of hydrogen transfer reactions involving acyclic radicals, a significant improvement in the stereoselectivity is observed when the two substituents at the stereogenic center alpha to the radical are imbedded in a cycle (''cycle effect''). A mechanistic rationale is discussed.

  DOI：

  10.1021/jo00084a040

文献信息

• Stereoselective Hydrogen Transfer Reactions Involving Acyclic Radicals. Tandem Substituted Tetrahydrofuran Formation and Stereoselective Reduction: Synthesis of the C17-C22 Subunit of Ionomycin
  作者：Y. Guindon、C. Yoakim、V. Gorys、W. W. Ogilvie、D. Delorme、J. Renaud、G. Robinson、J.-F. Lavallee、A. Slassi

  DOI：10.1021/jo00084a040

  日期：1994.3

  The tandem iodoetherification reaction and stereoselective reduction of acyclic radicals has been used in the stereocontrolled synthesis of substituted tetrahydrofurans. Such a tetrahydrofuran intermediate is regioselectively cleaved using Me(2)BBr to reveal the acyclic array 2 which represents the C-17-C-22 subunit of ionomycin. In experiments that provide for a better understanding of hydrogen transfer reactions involving acyclic radicals, a significant improvement in the stereoselectivity is observed when the two substituents at the stereogenic center alpha to the radical are imbedded in a cycle (''cycle effect''). A mechanistic rationale is discussed.
• Synthesis of the tetraene fragment of calyculins having natural configurations
  作者：Fumiaki Yokokawa、Yasumasa Hamada、Takayuki Shioiri

  DOI：10.1016/0040-4039(93)88104-q

  日期：1993.10

  Synthesis of the tetraene fragment 2, the C1–C12 portion, of calyculins (1f) has been accomplished by use of the Stille coupling of the vinyl iodide (C6-C12) unit 4 with the nitrile (C1–C5) unit 3 followed by converting to the vinyl iodide function according to the Barton's procedure.

  四烯片段的合成2中，C 1 -C 12部分，calyculins（的1 f）曾通过使用的Stille的乙烯基碘的（C联接完成6 -C 12）单元4与腈（C 1 - C 5）单元3，然后按照巴顿法将其转化为碘乙烯官能团。