(2S,9aS)-octahydro-2-methyl-(4H)-quinolizin-4-one | 928144-99-4

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 喹嗪类
• 英文名称: (2S,9aS)-octahydro-2-methyl-(4H)-quinolizin-4-one
• 英文别名: (2S,9aS)-2-methyl-octahydro-4H-quinolizin-4-one；(2S,9aS)-2-methyl-1,2,3,6,7,8,9,9a-octahydroquinolizin-4-one
• CAS: 928144-99-4
• 化学式: C₁₀H₁₇NO
• 分子量: 167.251
• InChiKey: LXUBYJSNDHGKFV-IUCAKERBSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.5
• 重原子数：
  12
• 可旋转键数：
  0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.9
• 拓扑面积：
  20.3
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  (2S,9aS)-octahydro-2-methyl-(4H)-quinolizin-4-one 在 sodium tetrahydroborate 作用下， 以 四氢呋喃 、 甲醇 、 甲苯 为溶剂， 反应 2.67h， 生成 (+)-cermizine C hydrochloride
  参考文献：
  名称：

  Total Synthesis of (−)-Senepodine G and (−)-Cermizine C

  摘要：

  An efficient, stereospecific synthesis of the alkaloids senepodine G (2 and cermizine C (1) has been completed using the BF3 center dot Et2O-promoted stereospecific addition of Me2CuLi to alpha,beta-unsaturated lactam 6 to provide lactam 3 the addition of MeMgBr followed by HCl to convert 3 to senepodine G (2) (six steps, 40% overall yield), and the stereospecific NaBH4 reduction of 2 to give cermizine C (1) (seven steps, 40% overall yield).

  DOI：

  10.1021/jo062067w
• 作为产物：
  描述：

  2-哌啶乙醇 在 copper(l) iodide 、 sodium hydride 、 potassium carbonate 、 戴斯-马丁氧化剂 、 (+)-10-camphorsulfonic acid 、 N,N-二异丙基乙胺 作用下， 以 四氢呋喃 、 乙醚 、 乙醇 、 二氯甲烷 为溶剂， 反应 21.08h， 生成 (2S,9aS)-octahydro-2-methyl-(4H)-quinolizin-4-one
  参考文献：
  名称：

  Total Synthesis of (−)-Senepodine G and (−)-Cermizine C

  摘要：

  An efficient, stereospecific synthesis of the alkaloids senepodine G (2 and cermizine C (1) has been completed using the BF3 center dot Et2O-promoted stereospecific addition of Me2CuLi to alpha,beta-unsaturated lactam 6 to provide lactam 3 the addition of MeMgBr followed by HCl to convert 3 to senepodine G (2) (six steps, 40% overall yield), and the stereospecific NaBH4 reduction of 2 to give cermizine C (1) (seven steps, 40% overall yield).

  DOI：

  10.1021/jo062067w

文献信息

• Preparation of Enantiopure Substituted Piperidines Containing 2-Alkene or 2-Alkyne Chains: Application to Total Syntheses of Natural Quinolizidine-Alkaloids
  作者：Guolin Cheng、Xinyan Wang、Deyong Su、Hui Liu、Fei Liu、Yuefei Hu

  DOI：10.1021/jo902615u

  日期：2010.3.19

  nonracemic Betti base as a chiral auxiliary. The key step is that the auxiliary residue was removed by a novel base-catalyzed N-debenzylation via a formation of o-quinone methide mechanism in stead of the traditional hydrogenolysis, by which the alkene or alkyne groups survived. By this method, ten 2-alkene- or 2-alkyne-containing chain substituted piperidines were prepared on the gram scale within

  通过使用非外消旋的Betti碱作为手性助剂，建立了制备对映体纯的含2个烯烃或2个炔烃的链取代哌啶的一般方法。关键步骤是代替传统的氢解反应，通过传统的氢解反应，通过邻甲基苯甲酸甲酯的形成，通过新颖的碱催化的N-脱苄基反应去除了辅助残基。通过这种方法，在数小时内以克为单位制备了十个含2-烯烃或2-炔烃的链取代的哌啶。为了证明该方法的有效性和产品的多功能性，使用（S）-2-烯丙基完成了天然生物碱（+）-peltierine，（-）-lasubine II和（+）-cermizine C的总合成--N -Boc-哌啶为通用成分。
• Enantioselective Approach to Quinolizidines: Total Synthesis of Cermizine D and Formal Syntheses of Senepodine G and Cermizine C
  作者：Nagarathanam Veerasamy、Erik C. Carlson、Nathan D. Collett、Mrinmoy Saha、Rich G. Carter

  DOI：10.1021/jo400324t

  日期：2013.5.17

  The formal syntheses of C5-epi-senepodine G and C5-epi-cermizine C have been accomplished through a novel diastereoselective, intramolecular amide Michael addition process. The total synthesis of cermizine D has been achieved through use of an organocatalyzed, heteroatom Michael addition to access a common intermediate. Additional key steps of this sequence include a matched, diastereoselective alkylation

  C的正式合成5 -外延-senepodine G和C 5 -外延-cermizine C 是通过一种新型的非对映选择性、分子内酰胺迈克尔加成过程完成的。cermizine D 的全合成是通过使用有机催化的杂原子迈克尔加成获得常见中间体来实现的。该序列的其他关键步骤包括使用碘甲基苯硫醚和砜-醛偶联/还原脱硫序列进行匹配的非对映选择性烷基化，以结合主要亚基。已经在功能密集的耦合伙伴上探索了 Hartwig 式 C-N 耦合的效用。已经研究了对 α,β-不饱和砜的非对映选择性共轭加成，这仅通过六步即可从市售起始材料中提供关键的砜中间体。N -Boc 保护的哌啶砜。
• Transition metal catalyzed stereodivergent synthesis of <i>syn</i>- and <i>anti</i>-δ-vinyl-lactams: formal total synthesis of (−)-cermizine C and (−)-senepodine G
  作者：Johannes Philipp Schmidt、Bernhard Breit

  DOI：10.1039/c8sc05502e

  日期：——

  catalyst allowed for the selective synthesis of the syn-δ-lactam. Conversely, a palladium catalyst led to the formation of the anti-δ-lactam in high selectivity. The new method shows high functional group compatibility and assorted synthetic transformations were demonstrated as well as its utility for the enantioselective formal total syntheses of (−)-cermizine C and (−)-senepodine G.

  报道了立体异构和非对映选择性过渡金属催化的提供δ-乙烯基-内酰胺的烯和炔的分子内加氢酰胺化。使用铑催化剂可以选择性合成顺式-δ-内酰胺。相反，钯催化剂导致以高选择性形成抗-δ-内酰胺。该新方法显示出高度的官能团相容性，并证明了各种合成转化及其对（-）-cermizine C和（-）-senepodine G的对映选择性形式全合成的实用性。
• Total Synthesis of (−)-Senepodine G and (−)-Cermizine C
  作者：Barry B. Snider、James F. Grabowski

  DOI：10.1021/jo062067w

  日期：2007.2.1

  An efficient, stereospecific synthesis of the alkaloids senepodine G (2 and cermizine C (1) has been completed using the BF3 center dot Et2O-promoted stereospecific addition of Me2CuLi to alpha,beta-unsaturated lactam 6 to provide lactam 3 the addition of MeMgBr followed by HCl to convert 3 to senepodine G (2) (six steps, 40% overall yield), and the stereospecific NaBH4 reduction of 2 to give cermizine C (1) (seven steps, 40% overall yield).