(-)-indolizidine 207A | 117982-91-9

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吲哚里西啶
• 英文名称: (-)-indolizidine 207A
• 英文别名: [5R,8R,8aS]-(-)-8-methyl-5-(pent-4-enyl)octahydroindolizine；(5R,8R,8aS)-8-methyl-5-pent-4-enyl-1,2,3,5,6,7,8,8a-octahydroindolizine
• CAS: 117982-91-9；141724-48-3
• 化学式: C₁₄H₂₅N
• 分子量: 207.359
• InChiKey: OHDBFRJCRJQLRN-MCIONIFRSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4
• 重原子数：
  15
• 可旋转键数：
  4
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.86
• 拓扑面积：
  3.2
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  (-)-indolizidine 207A 在 palladium on activated charcoal 氢气 作用下， 以 四氢呋喃 为溶剂， 反应 5.0h， 以93%的产率得到(-)-indolizidine 209B
  参考文献：
  名称：

  Enantiogenic total syntheses of (-)-indolizidines (bicyclic gephyrotoxins) 205A, 207A, 209B, and 235B via the intramolecular Diels-Alder reaction of a chiral N-acylnitroso compound

  摘要：

  A general protocol for the enantiogenic total syntheses of a series of the 5-substituted 8-methylindolizidine class of alkaloids from the arrow poison frog, i.e., (-)-indolizidines 205A (1), 207A (2), 209B (3), and 235B (4), is described, in which a key step is the asymmetric intramolecular Diels-Alder reaction of the chiral N-acylnitroso compound 8 leading to the bicyclic oxazinolactam 7 which was utilized as a versatile common chiral intermediate for the preparation of these alkaloids. Subsequent introduction of the C-5 (in future) side chain was elaborated by means of a completely stereocontrolled process involving a Grignard reaction followed by reduction with NaBH4 in acidic media. The bicyclic oxazines 20a, 24, and 26 thus obtained were then subjected to reductive N-O bond cleavage followed by cyclodehydration using PPh3/CBr4/Et3N, which provided the (-)-enantiomers of the title alkaloids.

  DOI：

  10.1021/jo00036a024
• 作为产物：
  描述：

  (2S,3R)-3,7-dimethyl-6-octene-1,2-diol 在 sodium hydroxide 、 sodium periodate 、 正丁基锂 、 sodium azide 、 silica gel 、 二异丁基氢化铝 、 三乙胺 、 对甲苯磺酰氯 、 三苯基膦 作用下， 以 四氯化碳 、 六甲基磷酰三胺 、 乙醚 、 二氯甲烷 、 乙酸乙酯 、 邻二氯苯 、 乙腈 为溶剂， 反应 50.08h， 生成 (-)-indolizidine 207A
  参考文献：
  名称：

  Enantioselective Synthesis of the Dendrobatid Alkaloid (-)-Indolizidine 207A

  摘要：

  An enantioselective synthesis of the Dendrobates alkaloid (-)-indolizidine 207A (1) is reported. The key intermediate in this synthesis is alcohol 6 (Scheme 1), prepared in four steps from geraniol with control of both relative and absolute configuration.

  DOI：

  10.1021/jo00108a011

文献信息

• Enantiopure <i>N</i>-Acyldihydropyridones as Synthetic Intermediates:  Asymmetric Syntheses of Indolizidine Alkaloids (−)-205A, (−)-207A, and (−)-235B
  作者：Daniel L. Comins、Donald H. LaMunyon、Xinghai Chen

  DOI：10.1021/jo971448u

  日期：1997.11.1

  addition of 4-(benzyloxy)butylmagnesium bromide, and vinyl triflate formation provided 13 in a stereoselective fashion. Catalytic reduction of the vinyl triflate moiety, simultaneous cleavage of the benzyl ether and Cbz groups, and cyclization to give amino alcohol 14 was effected via a one-pot reaction. Oxidation of 14 with the Dess-Martin reagent gave a 97% yield of amino aldehyde 4. Synthesis of each

  吲哚并立定生物碱（-）-205A，（-）-207A和（-）-235B的简明不对称合成是在11个步骤中以高度立体控制完成的。将4-（1-丁烯基）溴化镁加到1-酰基吡啶鎓盐5中，该盐由4-甲氧基-3-（三异丙基甲硅烷基）吡啶和（+）-反式-2-（α-枯基）环己醇的氯甲酸酯原位制备产生91％的非对映异构纯二氢吡啶酮6。6的氧化裂解和随后的还原提供了81％产率的醇7。除去手性助剂和TIPS组（NaOMe; 10％HCl），用BnOCOCCl进行N-酰化，并用NCS / Ph（3）P处理，得到氯化物10。在C-3处甲基化，铜介导的共轭加成4- （苄氧基）丁基溴化镁和三氟甲磺酸乙烯酯的形成以立体选择性方式提供了13。三氟甲基乙烯基部分的催化还原，通过一锅法反应同时裂解苄基醚和Cbz基团，以及环化得到氨基醇14。用Dess-Martin试剂氧化14时，氨基醛4的产率为97％。三种标题生物碱中的每一种的合
• A Convenient New Route to Piperidines, Pyrrolizidines, Indolizidines, and Quinolizidines by Cyclization of Acetylenic Sulfones with β- and γ-Chloroamines. Enantioselective Total Synthesis of Indolizidines <b>(</b><b>−</b><b>)-167B</b>, <b>(</b><b>−</b><b>)-209D</b>, <b>(</b><b>−</b><b>)-209B</b>, and <b>(</b><b>−</b><b>)-207A</b>
  作者：Thomas G. Back、Katsumasa Nakajima

  DOI：10.1021/jo000080p

  日期：2000.7.1

  the corresponding 2- or 2,6-disubstituted piperidines, while 2-(chloromethyl)pyrrolidines, 2-(2-chloroethyl)pyrrolidines, 2-(chloromethyl)piperidines, and 2-(2-chloroethyl)piperidines produced the corresponding 3-substituted pyrrolizidines, 5- or 3-substituted indolizidines, and 4-substituted quinolizidines, respectively. 8-Methyl-5-substituted indolizidines were also prepared from the appropriate methyl-substituted

  （L）-苯丙氨酸和（L）-蛋氨酸的甲酯通过其游离氨基与1-（对甲苯磺酰基）己炔进行共轭加成反应，随后将相应的酰胺阴离子进行分子内酰化和互变异构化，得到2-苄基- 5-正丁基-3-羟基-4-（对甲苯磺酰基）吡咯和5-正丁基-3-羟基-2-（2-甲硫基乙基）-4-（对甲苯磺酰基）吡咯。一系列无环和环状仲β-和γ-氯胺在炔属砜上的共轭加成在温和的条件下类似地进行。将所得的加合物在-78℃下用LDA在THF中的去质子化，并将所得的砜稳定的碳负离子进行分子内烷基化，得到环状烯胺砜。因此，无环的γ-氯烷基-苄胺提供了相应的2-或2，6-二取代的哌啶，而2-（氯甲基）吡咯烷，2-（2-氯乙基）吡咯烷，2-（氯甲基）哌啶和2-（2-氯乙基）哌啶产生相应的3-取代的吡咯烷，5-或3 -取代的吲哚嗪和4-取代的喹oli啶。还由适当的甲基取代的氯胺前体制备8-甲基-5-取代的吲哚并核苷。对映选择性合成是通过使用
• A Stereoselective Hydroamination Transform To Access Polysubstituted Indolizidines
  作者：Sergey V. Pronin、M. Greg Tabor、Daniel J. Jansen、Ryan A. Shenvi

  DOI：10.1021/ja211090n

  日期：2012.2.1

  Stereoselective, intramolecular, formal hydroamination of dienamines via directed hydroboration is reported. Four stereocenters are set in the process. Natural and unnatural indolizidine alkaloids can be synthesized from simple unsaturated amines using the title process.
• HOLMES, ANDREW B.;SMITH, ADRIAN L.;WILLIAMS, SIMON F.;HUGHES, LESLIE R.;L+, J. ORG. CHEM., 56,(1991) N, C. 1395-1405
  作者：HOLMES, ANDREW B.、SMITH, ADRIAN L.、WILLIAMS, SIMON F.、HUGHES, LESLIE R.、L+

  DOI：——

  日期：——
• Enantiogenic total syntheses of (-)-indolizidines (bicyclic gephyrotoxins) 205A, 207A, 209B, and 235B via the intramolecular Diels-Alder reaction of a chiral N-acylnitroso compound
  作者：Yuji Shishido、Chihiro Kibayashi

  DOI：10.1021/jo00036a024

  日期：1992.5

  A general protocol for the enantiogenic total syntheses of a series of the 5-substituted 8-methylindolizidine class of alkaloids from the arrow poison frog, i.e., (-)-indolizidines 205A (1), 207A (2), 209B (3), and 235B (4), is described, in which a key step is the asymmetric intramolecular Diels-Alder reaction of the chiral N-acylnitroso compound 8 leading to the bicyclic oxazinolactam 7 which was utilized as a versatile common chiral intermediate for the preparation of these alkaloids. Subsequent introduction of the C-5 (in future) side chain was elaborated by means of a completely stereocontrolled process involving a Grignard reaction followed by reduction with NaBH4 in acidic media. The bicyclic oxazines 20a, 24, and 26 thus obtained were then subjected to reductive N-O bond cleavage followed by cyclodehydration using PPh3/CBr4/Et3N, which provided the (-)-enantiomers of the title alkaloids.