(+/-)-2α-bromo-1,2,3,4,15,16-hexahydro-trans-1β,3α,4β-trihydroxycyclopentaphenanthren-17-one | 143216-84-6

• 分子结构分类: 有机化合物 - 苯类化合物 - 菲及其衍生物
• 英文名称: (+/-)-2α-bromo-1,2,3,4,15,16-hexahydro-trans-1β,3α,4β-trihydroxycyclopentaphenanthren-17-one
• 英文别名: 17H-Cyclopenta(a)phenanthren-17-one, 2-bromo-1,2,3,4,15,16-hexahydro-1,3,4-trihydroxy-, (1alpha,2beta,3beta,4alpha)-(+-)-；(1S,2R,3S,4R)-2-bromo-1,3,4-trihydroxy-1,2,3,4,15,16-hexahydrocyclopenta[a]phenanthren-17-one
• CAS: 143216-84-6
• 化学式: C₁₇H₁₅BrO₄
• 分子量: 363.208
• InChiKey: XYCQQVGAKQKJOX-WCXIOVBPSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.2
• 重原子数：
  22
• 可旋转键数：
  0
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.35
• 拓扑面积：
  77.8
• 氢给体数：
  3
• 氢受体数：
  4

上下游信息

反应信息

• 作为反应物：
  描述：

  (+/-)-2α-bromo-1,2,3,4,15,16-hexahydro-trans-1β,3α,4β-trihydroxycyclopentaphenanthren-17-one 在 sodium methylate 作用下， 以 四氢呋喃 、 甲醇 为溶剂， 反应 1.0h， 以80%的产率得到syn-1,2-epoxy-1,2,3,4,15,16-hexahydro-trans-3,4-dihydroxycyclopentaphenanthren-17-one
  参考文献：
  名称：

  Synthesis of the putative active metabolites of the cyclopenta[a]phenanthrenes. Synthesis of the trans-3,4-dihydro-3,4-diol and syn-3,4-diol 1,2-epoxide derivatives of the mutagen 15,16-dihydrocyclopenta[a]phenanthren-17-one

  摘要：

  The first synthesis of the trans-dihydro diol and syn-diol epoxide derivatives of a biologically active cyclopenta[a]phenanthrene is described. The cyclopenta[a]phenanthrene skeleton is rapidly and efficiently assembled utilizing the Lewis acid-catalyzed Diels-Alder reaction of 1,2-dihydro-7-methoxy-4-vinylnaphthalene (5) with an alpha-heterosubstituted cyclopentenone, a "cyclopentynone" equivalent. It was found that the Diels-Alder reaction of alpha-(phenylselenenyl)- (6a) or alpha-bromocyclopentenone (6b) with 5 in the presence of 1.5 euqiv of SnCl4 followed by elimination with hydrogen peroxide or DBU produced the key intermediate 15,16-dihydro-3-methoxycyclopenta[a]phenanthren-17-one (10) in 28% or 59% overall yield, respectively. The synthesis of the A-ring metabolites features the use of a unique methoxime protecting group for the 17-ketone. The deprotection of the 17-methoxime group of the highly acid-sensitive 3,4-trans-dihydro 3,4-diol bis(TBDMS) ether 15b was achieved through the use of the low-valent titanium reagent produced upon reduction of TiCl3.3THF by DIBAL-H (51%). Treatment of bis-(TBDMS) ether 16 with TBAF in THF provided the desired 3,4-trans-dihydro 3,4-diol (3) (83%), thus achieving the synthesis of 3 in 10 steps in 9.6% overall yield from 6b. In addition, the bay-region syn-3,4-diol 1,2-epoxide (4a) was also synthesized from 3 in two steps [(1) NBA in 1:5 H2O/DMSO, (2) NaOMe/THF] in 59% overall yield.

  DOI：

  10.1021/jo00047a030
• 作为产物：
  描述：

  15,16-dihydro-3-hydroxycyclopentaphenanthren-17-one methoxime 在 sodium tetrahydroborate 、 四氢呋喃氯化钛 、 (PhSeO)2O 、 四丁基氟化铵 、 水 、 氧气 、 二异丁基氢化铝 、 三乙胺 、 N-溴代乙酰胺 作用下， 以 四氢呋喃 、 乙醇 、 二甲基亚砜 、 甲苯 、 苯 为溶剂， 反应 126.5h， 生成 (+/-)-2α-bromo-1,2,3,4,15,16-hexahydro-trans-1β,3α,4β-trihydroxycyclopentaphenanthren-17-one
  参考文献：
  名称：

  Synthesis of the putative active metabolites of the cyclopenta[a]phenanthrenes. Synthesis of the trans-3,4-dihydro-3,4-diol and syn-3,4-diol 1,2-epoxide derivatives of the mutagen 15,16-dihydrocyclopenta[a]phenanthren-17-one

  摘要：

  The first synthesis of the trans-dihydro diol and syn-diol epoxide derivatives of a biologically active cyclopenta[a]phenanthrene is described. The cyclopenta[a]phenanthrene skeleton is rapidly and efficiently assembled utilizing the Lewis acid-catalyzed Diels-Alder reaction of 1,2-dihydro-7-methoxy-4-vinylnaphthalene (5) with an alpha-heterosubstituted cyclopentenone, a "cyclopentynone" equivalent. It was found that the Diels-Alder reaction of alpha-(phenylselenenyl)- (6a) or alpha-bromocyclopentenone (6b) with 5 in the presence of 1.5 euqiv of SnCl4 followed by elimination with hydrogen peroxide or DBU produced the key intermediate 15,16-dihydro-3-methoxycyclopenta[a]phenanthren-17-one (10) in 28% or 59% overall yield, respectively. The synthesis of the A-ring metabolites features the use of a unique methoxime protecting group for the 17-ketone. The deprotection of the 17-methoxime group of the highly acid-sensitive 3,4-trans-dihydro 3,4-diol bis(TBDMS) ether 15b was achieved through the use of the low-valent titanium reagent produced upon reduction of TiCl3.3THF by DIBAL-H (51%). Treatment of bis-(TBDMS) ether 16 with TBAF in THF provided the desired 3,4-trans-dihydro 3,4-diol (3) (83%), thus achieving the synthesis of 3 in 10 steps in 9.6% overall yield from 6b. In addition, the bay-region syn-3,4-diol 1,2-epoxide (4a) was also synthesized from 3 in two steps [(1) NBA in 1:5 H2O/DMSO, (2) NaOMe/THF] in 59% overall yield.

  DOI：

  10.1021/jo00047a030

文献信息

• Synthesis of the putative active metabolites of the cyclopenta[a]phenanthrenes. Synthesis of the trans-3,4-dihydro-3,4-diol and syn-3,4-diol 1,2-epoxide derivatives of the mutagen 15,16-dihydrocyclopenta[a]phenanthren-17-one
  作者：Stephen A. Woski、Masato Koreeda

  DOI：10.1021/jo00047a030

  日期：1992.10

  The first synthesis of the trans-dihydro diol and syn-diol epoxide derivatives of a biologically active cyclopenta[a]phenanthrene is described. The cyclopenta[a]phenanthrene skeleton is rapidly and efficiently assembled utilizing the Lewis acid-catalyzed Diels-Alder reaction of 1,2-dihydro-7-methoxy-4-vinylnaphthalene (5) with an alpha-heterosubstituted cyclopentenone, a "cyclopentynone" equivalent. It was found that the Diels-Alder reaction of alpha-(phenylselenenyl)- (6a) or alpha-bromocyclopentenone (6b) with 5 in the presence of 1.5 euqiv of SnCl4 followed by elimination with hydrogen peroxide or DBU produced the key intermediate 15,16-dihydro-3-methoxycyclopenta[a]phenanthren-17-one (10) in 28% or 59% overall yield, respectively. The synthesis of the A-ring metabolites features the use of a unique methoxime protecting group for the 17-ketone. The deprotection of the 17-methoxime group of the highly acid-sensitive 3,4-trans-dihydro 3,4-diol bis(TBDMS) ether 15b was achieved through the use of the low-valent titanium reagent produced upon reduction of TiCl3.3THF by DIBAL-H (51%). Treatment of bis-(TBDMS) ether 16 with TBAF in THF provided the desired 3,4-trans-dihydro 3,4-diol (3) (83%), thus achieving the synthesis of 3 in 10 steps in 9.6% overall yield from 6b. In addition, the bay-region syn-3,4-diol 1,2-epoxide (4a) was also synthesized from 3 in two steps [(1) NBA in 1:5 H2O/DMSO, (2) NaOMe/THF] in 59% overall yield.