(+)-austamide

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 哌嗪氮卓类
• 英文名称: (+)-austamide
• 英文别名: (9S,11S)-12,12-dimethylspiro[1,7-diazatricyclo[7.5.0.03,7]tetradeca-3,13-diene-11,2'-1H-indole]-2,3',8-trione
• 化学式: C₂₁H₂₁N₃O₃
• 分子量: 363.416
• InChiKey: LBFQJHHYMJAUKS-HRAATJIYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.5
• 重原子数：
  27
• 可旋转键数：
  0
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.38
• 拓扑面积：
  69.7
• 氢给体数：
  1
• 氢受体数：
  4

上下游信息

• 上游原料

  中文名称	英文名称	CAS号	化学式	分子量
  ——	dihydroaustamide	——	C21H23N3O3	365.432
  ——	(+)-hydroaustamide	——	C21H23N3O4	381.431
  ——	N-3-methyl-2-butenyl-N-(N'-Fmoc)-prolyl tryptophan methyl ester	274677-63-3	C37H39N3O5	605.734
  (3S,8aS)-3-[[2-(2-甲基丁-3-烯-2-基)-1H-吲哚-3-基]甲基]-2,3,6,7,8,8a-六氢吡咯并[2,1-f]吡嗪-1,4-二酮	deoxybrevianamide E	34610-68-9	C21H25N3O2	351.448

反应信息

• 作为产物：
  描述：

  3-甲基-2-丁烯醛 在 palladium diacetate 、 sodium tetrahydroborate 、 二甲基硫 、 氧气 、 sodium methylate 、 溶剂黄146 、 甲基磺酰氯 、 三乙胺 、 间氯过氧苯甲酸 、 过氧化苯甲酰 作用下， 以 四氢呋喃 、 甲醇 、 二氯甲烷 、 苯 为溶剂， 65.0 ℃ 、101.33 kPa 条件下， 反应 26.42h， 生成 (+)-austamide
  参考文献：
  名称：

  A Short Synthetic Route to (+)-Austamide, (+)-Deoxyisoaustamide, and (+)-Hydratoaustamide from a Common Precursor by a Novel Palladium-Mediated Indole → Dihydroindoloazocine Cyclization

  摘要：

  The first synthesis of (+)-austamide (1), (+)-deoxyisoaustamide (2), and (+)-hydratoaustamide (10) by a very direct route is described (Scheme 1). Starting from tryptophan methyl ester (3) intermediate 5 is generated in two steps in >98% overall yield. The key step in the synthesis is a novel cyclization of 5 involving organopalladium intermediates which gives the dihydroazocine 6. From this key intermediate the target structures are accessible in just a few steps as shown in Scheme 1. The remarkable conversion of 5 --> 6 can be rationalized by the mechanistic pathway shown in Scheme 2 that involves a multistep sequence which includes palladation, cyclization, and rearrangement.

  DOI：

  10.1021/ja026663t

文献信息

• Reverse Prenyl Transferases Exhibit Poor Facial Discrimination in the Biosynthesis of Paraherquamide A, Brevianamide A, and Austamide
  作者：Emily M. Stocking、Robert M. Williams、Juan F. Sanz-Cervera

  DOI：10.1021/ja993593q

  日期：2000.9.1

  The mode of attachment of dimethylallyl pyrophosphate (DMAPP) in the biosynthesis of the indole alkaloids paraherquamide A, austamide, and brevianamide A has been studied. Feeding experiments or, Penicillium fellutanum, Penicillium brevicompactum, and Aspergillus ustus using [C-13(2)]-acetate showed isotopic scrambling of the geminal methyl groups originating from C-2 of the indole ring precursors in paraherquamide A, brevianamide A, and austamide biosynthesis. The labeling patterns suggest that the methyl groups of dimethylallyl pyrophosphate become equivalent during the biosyntheses; a non-face-selective, S-N' mechanism has been invoked to account for these observations.
• A Short Synthetic Route to (+)-Austamide, (+)-Deoxyisoaustamide, and (+)-Hydratoaustamide from a Common Precursor by a Novel Palladium-Mediated Indole → Dihydroindoloazocine Cyclization
  作者：Phil S. Baran、E. J. Corey

  DOI：10.1021/ja026663t

  日期：2002.7.1

  The first synthesis of (+)-austamide (1), (+)-deoxyisoaustamide (2), and (+)-hydratoaustamide (10) by a very direct route is described (Scheme 1). Starting from tryptophan methyl ester (3) intermediate 5 is generated in two steps in >98% overall yield. The key step in the synthesis is a novel cyclization of 5 involving organopalladium intermediates which gives the dihydroazocine 6. From this key intermediate the target structures are accessible in just a few steps as shown in Scheme 1. The remarkable conversion of 5 --> 6 can be rationalized by the mechanistic pathway shown in Scheme 2 that involves a multistep sequence which includes palladation, cyclization, and rearrangement.