(1S,6R)-3-(tert-butyldimethylsiloxymethyl)-4-(prop-1-enyl)-7-oxabicyclo[4.1.0]hept-3-ene-2,5-dione | 675107-20-7

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (1S,6R)-3-(tert-butyldimethylsiloxymethyl)-4-(prop-1-enyl)-7-oxabicyclo[4.1.0]hept-3-ene-2,5-dione
• CAS: 675107-20-7
• 化学式: C₁₆H₂₄O₄Si
• 分子量: 308.45
• InChiKey: XSIUTSUNEWMEBH-MHKRFPNSSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.8
• 重原子数：
  21.0
• 可旋转键数：
  4.0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.62
• 拓扑面积：
  55.9
• 氢给体数：
  0.0
• 氢受体数：
  4.0

反应信息

• 作为反应物：
  描述：

  (1S,6R)-3-(tert-butyldimethylsiloxymethyl)-4-(prop-1-enyl)-7-oxabicyclo[4.1.0]hept-3-ene-2,5-dione 在 Dowex(R)50W-X₄ 作用下， 以 甲醇 为溶剂， 反应 11.0h， 以81%的产率得到(1S,6R)-3-(hydroxymethyl)-4-(prop-1-enyl)-7-oxabicyclo[4.1.0]hept-3-ene-2,5-dione
  参考文献：
  名称：

  Different Reaction Modes for the Oxidative Dimerization of Epoxyquinols and Epoxyquinones. Importance of Intermolecular Hydrogen-Bonding

  摘要：

  An oxidative dimerization reaction, involving the three successive steps of oxidation, 6pi-electrocyclization, and Diels-Alder reaction, has been experimentally and theoretically investigated for the three 2-alkenyl-3-hydroxymethyl-2-cyclohexen-1-one derivatives epoxyquinol 3, epoxyquinone 6, and cyclohexenone 10. Of the sixteen possible modes of the oxidation/6pi-electrocylization/Diels-Alder reaction cascade for the epoxyquinone 6, and eight for the cyclohexenone 10, only the endo-anti(epoxide)-anti(Me)-hetero and endo-anti(Me)-hetero modes are, respectively, observed, while both endo-anti(epoxide)-anti(Me)-hetero and exo-anti(epoxide)-anti(Me)-homo reaction modes occur with the epoxyquinol 3. Intermolecular hydrogen-bonding is found to be the key cause of formation of both epoxyquinols A and B with 3, although epoxyquinone 6 and cyclohexenone 10 both gave selectively only the epoxyquinol A-type product. In the dimerization of epoxyquinol 3, two monomer 2H-pyrans 5 interact with each other to afford intermediate complex 28 or 29 stabilized by hydrogen-bonding, from which Diels-Alder reaction proceeds. Theoretical calculations have also revealed the differences in the reaction profiles of epoxyquinone 6 and cyclohexenone 10. Namely, the rate-determining step of the former is the Diels-Alder reaction, while that of the latter is the 6pi-electrocyclization.

  DOI：

  10.1021/jo0355303
• 作为产物：
  描述：

  (1R,5S,6R)-4-(tert-butyldimethylsiloxymethyl)-5-hydroxy-3-(prop-1-enyl)-7-oxabicyclo[4.1.0]hept-3-en-2-one 在 戴斯-马丁氧化剂 作用下， 以 二氯甲烷 为溶剂， 反应 0.17h， 以90%的产率得到(1S,6R)-3-(tert-butyldimethylsiloxymethyl)-4-(prop-1-enyl)-7-oxabicyclo[4.1.0]hept-3-ene-2,5-dione
  参考文献：
  名称：

  Different Reaction Modes for the Oxidative Dimerization of Epoxyquinols and Epoxyquinones. Importance of Intermolecular Hydrogen-Bonding

  摘要：

  An oxidative dimerization reaction, involving the three successive steps of oxidation, 6pi-electrocyclization, and Diels-Alder reaction, has been experimentally and theoretically investigated for the three 2-alkenyl-3-hydroxymethyl-2-cyclohexen-1-one derivatives epoxyquinol 3, epoxyquinone 6, and cyclohexenone 10. Of the sixteen possible modes of the oxidation/6pi-electrocylization/Diels-Alder reaction cascade for the epoxyquinone 6, and eight for the cyclohexenone 10, only the endo-anti(epoxide)-anti(Me)-hetero and endo-anti(Me)-hetero modes are, respectively, observed, while both endo-anti(epoxide)-anti(Me)-hetero and exo-anti(epoxide)-anti(Me)-homo reaction modes occur with the epoxyquinol 3. Intermolecular hydrogen-bonding is found to be the key cause of formation of both epoxyquinols A and B with 3, although epoxyquinone 6 and cyclohexenone 10 both gave selectively only the epoxyquinol A-type product. In the dimerization of epoxyquinol 3, two monomer 2H-pyrans 5 interact with each other to afford intermediate complex 28 or 29 stabilized by hydrogen-bonding, from which Diels-Alder reaction proceeds. Theoretical calculations have also revealed the differences in the reaction profiles of epoxyquinone 6 and cyclohexenone 10. Namely, the rate-determining step of the former is the Diels-Alder reaction, while that of the latter is the 6pi-electrocyclization.

  DOI：

  10.1021/jo0355303

文献信息

• Novel non-peptide inhibitors targeting death receptor-Mediated apoptosis
  作者：Hideaki Kakeya、Yasunobu Miyake、Mitsuru Shoji、Satoshi Kishida、Yujiro Hayashi、Takao Kataoka、Hiroyuki Osada

  DOI：10.1016/j.bmcl.2003.08.003

  日期：2003.11

  We have previously reported that ECH, (2R, 3R, 4S)-2,3-epoxy-4-hydroxy-5-hydroxymethyl-6-(1E)-propenyl-cyclohex-5-en-1-one inhibits Fas-mediated apoptosis by blocking self-activation of pro-caspase-8 in the death-inducing signaling complex (DISC). A series of ECH derivatives were asymmetrically synthesized via key synthetic intermediates obtained from lipase-catalyzed kinetic resolution. Inhibitory activities of the derivatives towards death receptor-mediated apoptosis both in type I and type 11 cells were investigated, revealing that novel non-peptide inhibitors, RKTS-33 and RKTS-34, are effective as ECH. (C) 2003 Elsevier Ltd. All rights reserved.