(+/-)-3-methoxy-14β-estra-1,3,5(10),9(11)-tetraen-17-one | 966-46-1

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 类固醇和类固醇衍生物
• 英文名称: (+/-)-3-methoxy-14β-estra-1,3,5(10),9(11)-tetraen-17-one
• 英文别名: (8S,13S,14R)-3-methoxy-13-methyl-7,8,12,14,15,16-hexahydro-6H-cyclopenta[a]phenanthren-17-one
• CAS: 966-46-1；1670-49-1；83829-17-8；84710-10-1；95585-35-6；98049-50-4；143167-95-7；143167-96-8
• 化学式: C₁₉H₂₂O₂
• 分子量: 282.382
• InChiKey: AGAVSENPCRLEAB-LMMKCTJWSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.4
• 重原子数：
  21
• 可旋转键数：
  1
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.53
• 拓扑面积：
  26.3
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  (+/-)-3-methoxy-14β-estra-1,3,5(10),9(11)-tetraen-17-one 在 盐酸 、 palladium diacetate 、 三甲基氯硅烷 、 lithium diisopropyl amide 作用下， 以 甲醇 、 二氯甲烷 为溶剂， 反应 11.0h， 生成 3-methoxy-14-estra-1,3,5(10),8,15-pentaen-17-one
  参考文献：
  名称：

  An enantioselective version of the AB+B→ABCD-type steroid total synthesis

  摘要：

  Diene 1 and dienophile 4a in a Diels/Alder reaction mediated by a chiral ligand-modified Lewis acid enantioselectively furnish adduct 5a (chem. yield. 64%, e.e.: 73%), which after partial deoxygenation and final enantioselection by recrystallization affords 5b. The latter compound can easily be converted via Torgov's pentaenone 6a into estrogens or progestogens.

  DOI：

  10.1016/s0040-4039(00)92517-6
• 作为产物：
  描述：

  甲基环戊烯醇酮 在 正丁基锂 、 异丁醇 、 氯化二乙基铝 、 S-甲基-S-苯基-N-甲基亚砜亚胺 作用下， 以 二氯甲烷 为溶剂， 反应 16.0h， 生成 (+/-)-3-methoxy-14β-estra-1,3,5(10),9(11)-tetraen-17-one
  参考文献：
  名称：

  An enantioselective version of the AB+B→ABCD-type steroid total synthesis

  摘要：

  Diene 1 and dienophile 4a in a Diels/Alder reaction mediated by a chiral ligand-modified Lewis acid enantioselectively furnish adduct 5a (chem. yield. 64%, e.e.: 73%), which after partial deoxygenation and final enantioselection by recrystallization affords 5b. The latter compound can easily be converted via Torgov's pentaenone 6a into estrogens or progestogens.

  DOI：

  10.1016/s0040-4039(00)92517-6

文献信息

• Cationic Chiral Fluorinated Oxazaborolidines. More Potent, Second-Generation Catalysts for Highly Enantioselective Cycloaddition Reactions
  作者：Karla Mahender Reddy、Eswar Bhimireddy、Barla Thirupathi、Simon Breitler、Shunming Yu、E. J. Corey

  DOI：10.1021/jacs.6b00100

  日期：2016.2.24

  placement of fluorine substituents in the chiral ligand. This approach has led to a new, second-generation family of chiral oxazaborolidinium cationic species which can be used to effect many Diels-Alder reactions in >95% yield and >95% ee using catalyst loadings at the 1-2 mol % level. The easy recovery of the chiral ligand makes the application of these new catalysts especially attractive for large-scale

  手性配体与路易斯酸金属衍生物的配位是对映选择性亲电催化的一种有用策略，通常导致催化活性水平低于原始未络合化合物的催化活性水平。通过进一步将质子或强路易斯酸连接到复合物上进行活化提供了一种克服手性配体失活作用的方法。本文所述的研究表明，通过在手性配体中明智地放置氟取代基，可以进一步提高催化活性。这种方法产生了一个新的第二代手性 oxazaborolidinium 阳离子物种家族，使用 1-2 mol% 水平的催化剂负载量，该物种可用于以 >95% 的产率和 >95% 的 ee 进行许多 Diels-Alder 反应。
• Total Synthesis with a Chirogenic Opening Move Demonstrated on Steroids with Estrane or 18a-Homoestrane Skeleton
  作者：Gerhard Quinkert、Michael Del Grosso、Astrid Döring、Wolfgang Döring、Ralf I. Schenkel、Markus Bauch、Gernot T. Dambacher、Jan W. Bats、Gottfried Zimmermann、Gerd Dürner

  DOI：10.1002/hlca.19950780524

  日期：1995.8.9

  A concept of first choice for the synthesis of the title compounds had been proposed by Dane in the late 1930s. It was soon turned down, because the opening move–a chirogenic Diels-Alder reaction – did not work. With Lewis acids as mediators, however, a successful start has been achieved now. With Ti complexes of chelating ligands (Seebach's TADDOLs (= α,α,α′,α′-tetraaryl-1,3-dioxolane-4,5-dimethanols))

  Dane在1930年代后期提出了合成标题化合物的首选方法。很快就被拒绝了，因为开场动作–致色Diels - Alder反应–无效。但是，以路易斯酸为介质，现在已经取得了成功的开始。使用螯合配体的Ti络合物（Seebach 's TADDOLs（=α，α，α'，α'-四芳基-1,3-二氧戊环-4,5-二甲醇）），确实发生了所需加合物的对映选择性形成。已经完成了2和3a的有效总合成。
• Highly Enantioselective [4 + 2] Cycloaddition Reactions Catalyzed by a Chiral <i>N</i>-Methyl-oxazaborolidinium Cation
  作者：Eda Canales、E. J. Corey

  DOI：10.1021/ol8011502

  日期：2008.8.7

  The reaction of lithium aryl borohydrides with salts of beta-amino alcohols provides a new route for the synthesis of oxazaborolidines. This method also leads to the first synthesis of hitherto elusive N-methyl oxazaborolidine cations, specifically the cationic proline derivative 3. Compound 3 is a strong chiral Lewis acid which is very effective for catalysis of [4 + 2]-cycloaddition reactions in good yield and with high enantioselectivity. Several diverse examples illustrate the scope of these catalytic reactions.