((1S*,2S*)-cyclohex-4-ene-1,2-diyl)bis(methylene) dibenzoate | 141389-84-6

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: ((1S*,2S*)-cyclohex-4-ene-1,2-diyl)bis(methylene) dibenzoate
• 英文别名: (4S,5S)-4,5-bis(benzoyloxymethyl)-1-cyclohexene；[(1S,6S)-6-(benzoyloxymethyl)cyclohex-3-en-1-yl]methyl benzoate
• CAS: 141389-84-6
• 化学式: C₂₂H₂₂O₄
• 分子量: 350.414
• InChiKey: CCWLJRVYOBMPHB-WOJBJXKFSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5
• 重原子数：
  26
• 可旋转键数：
  8
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.27
• 拓扑面积：
  52.6
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  ((1S*,2S*)-cyclohex-4-ene-1,2-diyl)bis(methylene) dibenzoate 在 palladium on activated charcoal 盐酸 、 DIAD 、 氨 、 氢气 、 1,8-二氮杂双环[5.4.0]十一碳-7-烯 、 间氯过氧苯甲酸 、 三苯基膦 作用下， 以 甲醇 、 二氯甲烷 、 甲苯 为溶剂， 反应 145.5h， 生成 9-[(1S,3S,4S)-3,4-bis(hydroxymethyl)-cyclohexyl]-adenine
  参考文献：
  名称：

  Synthesis of Enantiomerically Pure Bis(hydroxymethyl)-Branched Cyclohexenyl and Cyclohexyl Purines as Potential Inhibitors of HIV

  摘要：

  The synthesis of the enantiomerically pure bis(hydroxymethyl)-branched cyclohexenyl and cyclohexyl purines is described. Racemic trans-4,5-bis(methoxycarbonyl)cyclohexene [(+/-)-6] was reduced with lithium aluminum hydride to give the racemic diol (+/-)-7. Resolution of(+/-)-7 via a transesterification process using lipase from Pseudomonas sp. (SAM-II) gave both diols in enantiomerically pure form. The enantiomerically pure diol (S,S)-7 was benzoylated and epoxidized to give the epoxide 9. Treatment of the epoxide 9 with trimethylsilyl trifluoromethanesulfonate and 1,5-diazabicyclo-[5.4.0]undec-5-ene followed by dilute hydrochloric acid gave (LR,4S,5R)-4,5-bis[(benzoyloxy)methyl]-1-hydroxycyclohex-2-ene (10). Acetylation of 10 gave (LR,4S,5R)-1-acetoxy-4,5-bis[(benzoyloxy)-methyl]cyclohex-2-ene (11). (1R,4S,5R)-1-Acetoxy-4,5-bis[(benzoyloxy)methyl]cyclohex-2-ene (11) was converted to the adenine derivative 12 and guanine derivative 13 via palladium(0)-catalyzed coupling with adenine and 2-amino-6-chloropurine, respectively. Hydrogenation of 12 and 13 gave the correspondning saturated adenine derivative 14 and guanine derivative 15. (1R,4S,5R)-4,5-Bis[(benzoyloxy)methyl]-1-hydroxycyclohex-2-ene (10) was converted to the adenine derivative 16 and guanine derivative 1? via coupling with 6-chloropurine and 2-amino-6-chloropurine, respectively, using a modified Mitsunobu procedure. Hydrogenation of 16 and 17 gave the corresponding saturated adenine derivative 18 and guanine derivative 19. Compounds 12-19 were evaluated for activity against human immunodeficiency virus (HIV), but mere found to be inactive. Further biological testings are underway.

  DOI：

  10.1021/jo9603542
• 作为产物：
  描述：

  rac-trans-4,5-bis(methoxycarbonyl)cyclohexene 在 吡啶 、 lithium aluminium tetrahydride 作用下， 以 四氢呋喃 为溶剂， 反应 5.5h， 生成 ((1S*,2S*)-cyclohex-4-ene-1,2-diyl)bis(methylene) dibenzoate
  参考文献：
  名称：

  Synthesis of Enantiomerically Pure Bis(hydroxymethyl)-Branched Cyclohexenyl and Cyclohexyl Purines as Potential Inhibitors of HIV

  摘要：

  The synthesis of the enantiomerically pure bis(hydroxymethyl)-branched cyclohexenyl and cyclohexyl purines is described. Racemic trans-4,5-bis(methoxycarbonyl)cyclohexene [(+/-)-6] was reduced with lithium aluminum hydride to give the racemic diol (+/-)-7. Resolution of(+/-)-7 via a transesterification process using lipase from Pseudomonas sp. (SAM-II) gave both diols in enantiomerically pure form. The enantiomerically pure diol (S,S)-7 was benzoylated and epoxidized to give the epoxide 9. Treatment of the epoxide 9 with trimethylsilyl trifluoromethanesulfonate and 1,5-diazabicyclo-[5.4.0]undec-5-ene followed by dilute hydrochloric acid gave (LR,4S,5R)-4,5-bis[(benzoyloxy)methyl]-1-hydroxycyclohex-2-ene (10). Acetylation of 10 gave (LR,4S,5R)-1-acetoxy-4,5-bis[(benzoyloxy)-methyl]cyclohex-2-ene (11). (1R,4S,5R)-1-Acetoxy-4,5-bis[(benzoyloxy)methyl]cyclohex-2-ene (11) was converted to the adenine derivative 12 and guanine derivative 13 via palladium(0)-catalyzed coupling with adenine and 2-amino-6-chloropurine, respectively. Hydrogenation of 12 and 13 gave the correspondning saturated adenine derivative 14 and guanine derivative 15. (1R,4S,5R)-4,5-Bis[(benzoyloxy)methyl]-1-hydroxycyclohex-2-ene (10) was converted to the adenine derivative 16 and guanine derivative 1? via coupling with 6-chloropurine and 2-amino-6-chloropurine, respectively, using a modified Mitsunobu procedure. Hydrogenation of 16 and 17 gave the corresponding saturated adenine derivative 18 and guanine derivative 19. Compounds 12-19 were evaluated for activity against human immunodeficiency virus (HIV), but mere found to be inactive. Further biological testings are underway.

  DOI：

  10.1021/jo9603542

文献信息

• IBX as a catalyst for dehydration of hydroperoxides: green entry to α,β-unsaturated ketones <i>via</i> oxygenative allylic transposition
  作者：Tetsuya Kuga、Yusuke Sasano、Yoshiharu Iwabuchi

  DOI：10.1039/c7cc08957k

  日期：——

  A catalytic transformation of allylic hydroperoxides into α,β-unsaturated carbonyl compounds using IBX as a dehydration catalyst is described. The combination of a singlet oxygen ene reaction and the IBX-catalyzed dehydration provides α,β-unsaturated carbonyl compounds from alkenes via oxygenative allylic transposition with H2O as the only byproduct.

  描述了使用IBX作为脱水催化剂将烯丙基氢过氧化物催化转化为α，β-不饱和羰基化合物。单线态氧烯反应和IBX催化的脱水相结合，通过H 2 O作为唯一副产物的氧化烯丙基转移，从烯烃中获得α，β-不饱和羰基化合物。
• Synthesis of 1,3-Cycloalkadienes from Cycloalkenes: Unprecedented Reactivity of Oxoammonium Salts
  作者：Shota Nagasawa、Yusuke Sasano、Yoshiharu Iwabuchi

  DOI：10.1002/anie.201607752

  日期：2016.10.10

  Few methods allow for the direct conversion of cycloalkenes into cycloalkadienes with high chemo‐ and regioselectivity. Herein, we report a convenient one‐pot process for this transformation that involves the unprecedented N‐preferential group transfer of N‐oxoammonium salts to cycloalkenes, followed by Cope elimination, to afford cycloalkadienes at room temperature and pressure.

  很少有方法能够将环烯烃直接转化为具有高化学和区域选择性的环烷二烯。在此，我们提出一个方便的一锅法用于该转化，其涉及的前所未有的N-优先基团转移Ñ -oxoammonium盐环烯烃，随后柯普消除，以得到在室温和压力环二烯。
• Adenine and guanine derivatives for the treatment of hepatitis virus
  申请人：Nippon Kayaku Kabushiki Kaisha

  公开号：US05374625A1

  公开（公告）日：1994-12-20

  A novel nucleic acid derivative represented by the following general formula (I) and physiologically acceptable salt thereof which are expected to have an antiviral activity: ##STR1## wherein B represents a nucleic acid base derivative; A.sup.1 and A.sup.2 represent, independently of each other, OR.sup.1 or OCOR.sup.1 ; R.sup.1 represents a hydrogen atom, a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group; l represents a number of 0 or 1; and m and n each represents an integer of 0-2; provided that when l and m are 0, n is 0 or 2.

  由以下一般式（I）表示的新型核酸衍生物及其生理上可接受的盐，预计具有抗病毒活性：##STR1## 其中B代表核酸碱基衍生物；A.sup.1和A.sup.2分别表示OR.sup.1或OCOR.sup.1；R.sup.1代表氢原子、取代或未取代的烷基或取代或未取代的芳基；l表示0或1的数字；m和n分别表示0-2的整数；但当l和m为0时，n为0或2。
• Novel nucleic acid derivatives
  申请人：Nippon Kayaku Kabushiki Kaisha

  公开号：EP0468352A2

  公开（公告）日：1992-01-29

  A novel nucleic acid derivative represented by the following general formula (I) and physiologically acceptable salt thereof which are expected to have an antiviral activity: wherein B represents a nucleic acid base derivative; A1 and A2 represent, independently of each other, OR1 or OCOR1; R1 represents a hydrogen atom, a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group; ℓ represents a number of 0 or 1; and m and n each represents an integer of 0-2; provided that when ℓ and m are 0, n is 0 or 2.

  由以下通式(I)代表的新型核酸衍生物及其生理上可接受的盐，有望具有抗病毒活性： 其中 B 代表核酸碱基衍生物；A1 和 A2 各自代表 OR1 或 OCOR1；R1 代表氢原子、取代或未取代的烷基或取代或未取代的芳基；ℓ 代表 0 或 1 的数字；m 和 n 各自代表 0-2 的整数；但当 ℓ 和 m 为 0 时，n 为 0 或 2。
• US5374625A
  申请人：——

  公开号：US5374625A

  公开（公告）日：1994-12-20