methyl N^α-benzyl-N^α-(tert-butoxycarbonyl)-L-tryptophanate | 219558-74-4

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羧酸及其衍生物
• 英文名称: methyl N^α-benzyl-N^α-(tert-butoxycarbonyl)-L-tryptophanate
• 英文别名: N^bBoc-N^b-benzyltryptophan methyl ester；methyl (2S)-2-[benzyl-[(2-methylpropan-2-yl)oxycarbonyl]amino]-3-(1H-indol-3-yl)propanoate
• CAS: 219558-74-4
• 化学式: C₂₄H₂₈N₂O₄
• 分子量: 408.497
• InChiKey: XBDPCXACSMXWIX-NRFANRHFSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.6
• 重原子数：
  30
• 可旋转键数：
  9
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.33
• 拓扑面积：
  71.6
• 氢给体数：
  1
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  methyl N^α-benzyl-N^α-(tert-butoxycarbonyl)-L-tryptophanate 在 potassium osmate(VI) 、 钾硼氢 、 potassium metaperiodate 、 三氟甲磺酸三甲基硅酯 、 氨 、 水 、 三乙胺 、 N,N-二异丙基乙胺 、 对苯二酚 、 苯甲酸 、 三氟乙酸酐 、 lithium chloride 作用下， 以 甲醇 、 乙醇 、 二氯甲烷 、 水 、 N,N-二甲基甲酰胺 、 苯 为溶剂， 反应 147.67h， 生成 (+/-)-methyl (2S*,3aS*,5R*,11bR*)-3-benzyl-2,3,3a,4,5,7-hexahydro-5-formyl-1H-pyrrolo<2,3-d>carbazole-6-carboxylate
  参考文献：
  名称：

  Syntheses of Strychnan- and Aspidospermatan-Type Alkaloids. 10. An Enantioselective Synthesis of (−)-Strychnine through the Wieland−Gumlich Aldehyde

  摘要：

  Condensations of L-tryptophan-derived 2-[(methoxycarbonyl)methyl]-3-[2(S)-(benzyloxycarbonyl)- 2-(N-b-benzylamino)ethyl]indole (6) with 4,4-dimethoxyacrolein or with 2,4-hexadienal, followed by removal of the tryptophanyl ester function, respectively gave the tetracyclic acetal (-)-methyl (2S, 3aS,5R,11bR)-3-benzyl-2,3,3a,4,5,7-hexahydro-5-(dimethoxymethyl)-1H-pyrrolo[2,3-d]carbazole-6-carboxylate (10) or the tetracyclic olefin (-)-methyl (2S,3aS,5R,11bR)-3-benzyl-2,3,3a,4,5,7-hexahydro-5-(1-propenyl)-1H-pyrrolo[2,3-d]carbazole-6-carboxylate (14). Their respective hydrolysis or oxidation provided, enantioselectively, the tetracyclic aldehyde (-)-methyl (2S,3aS,5R,11bR)3-benzyl-2,3,3a,4,5,7-hexahydro-5-formyl-1H-pyrrolo[2,3-d]carbazole-6-carboxylate (5). Its reaction with tri-n-butyl-1-(ethoxy)ethoxymethyltin and n-butyllithium, followed by oxidation of the resultant alcohol (-)-methyl (2S,3aS,5R,11bR)-3-benzyl-2,3,3a,4,5,7-hexahydro-5-(1 xi-hydroxy-2-((1-ethoxy-ethoxy))ethyl-1H-pyrrolo[2,3-d]carbazole-6-carboxylate (16) and cyclization furnished the pentacyclic ketone (-)-methyl (2S,3aS,5R,11bR)-3-benzyl-2,3,3a,4,5,7-hexahydro-3,5-ethano-12-oxo-1H-pyrrolo-2,3-d]carbazole-6-carboxylate (15). A Horner-Emmons condensation led to the unsaturated esters (-)-methyl (2S,3aS,5R,11bR)-3-benzyl-2,3,3a,4,5,7-hexahodro-3,5-ethano-12-(E and Z)-[(methoxycarbonyl)-methylene]-1H-pyrrolo[2,3-d]carbazole-6-carboxylates(19 and 20) with 17:1 E/Z selectivity. Reductions of the ester and vinylogous urethane functions in 19 led to the Wieland-Gumlich aldehyde 3 as a 6:1 anomeric hemiacetal mixture. Its condensation with malonic acid provided (-)-strychnine (1) in 5.3% overall yield and 14 steps from the tryptophan derivative 6.

  DOI：

  10.1021/jo9813989
• 作为产物：
  描述：

  L-色氨酸甲酯盐酸盐 在 sodium tetrahydroborate 、 potassium carbonate 、 三乙胺 作用下， 以 甲醇 、 乙醚 、 二氯甲烷 、 水 为溶剂， 反应 30.0h， 生成 methyl N^α-benzyl-N^α-(tert-butoxycarbonyl)-L-tryptophanate
  参考文献：
  名称：

  Oxazolidinones and 2,5-Dihydrofurans via Zinc-Catalyzed Regioselective Allenylation Reactions of l-α-Amino Aldehydes

  摘要：

  The simultaneous control of diastereoselectivity and regioselectivity in Zn-catalyzed allenylation reactions of N-protected L-alpha-amino aldehydes is reported. A reversal in diastereoselectivity could be realized by variation of the alpha-amino aldehyde protecting groups. A range of 1-allenyl-2-amino alcohols were obtained with excellent regioselectivity and converted to oxazolidinones and dihydrofurans. Many of which could be isolated as single diastereoisomers and without significant erosion of ee, making this a practical catalytic synthesis of highly functionalized heterocycles.

  DOI：

  10.1021/acs.joc.7b00969

文献信息

• Fenton chemistry enables the catalytic oxidative rearrangement of indoles using hydrogen peroxide
  作者：Guodong Zhao、Lixin Liang、Eryu Wang、Shaoyan Lou、Rui Qi、Rongbiao Tong

  DOI：10.1039/d1gc00297j

  日期：——

  Oxidative rearrangement of indoles is an important transformation to yield 2-oxindoles and spirooxindoles, which are present in many pharmaceutical agents and bioactive natural products. Previous oxidation methods show either broad applicability or greenness but rarely achieve both. Reported is the discovery of Fenton chemistry-enabled green catalytic oxidative rearrangement of indoles, which has wide substrate

  吲哚的氧化重排是产生2-氧吲哚和螺硫辛醇的重要转化，其存在于许多药剂和生物活性天然产物中。先前的氧化方法显示出广泛的适用性或绿色，但很少能同时实现。据报道发现了芬顿化学法使吲哚的绿色催化氧化重排的发现，它具有广泛的底物范围（42个例子）和绿色（同时水是唯一的化学计量副产物）。详细的机理研究表明，芬顿化学产生的羟基自由基进一步将溴化物氧化为反应性溴化物种（RBS：溴或次溴酸）。这原位生成的RBS是氧化重排的真正催化剂。重要的是，RBS在中性条件下产生，这解决了许多卤代过氧化物酶模拟物的长期存在的问题，这些模拟物需要强酸才能用过氧化氢氧化溴化物。预期该新的催化芬顿卤化物系统将在有机合成中得到广泛的应用。
• 一种制备氧化吲哚类衍生物的绿色方法
  申请人：香港科技大学

  公开号：CN113024438A

  公开（公告）日：2021-06-25

  本发明涉及绿色有机合成技术领域，提供了一种制备氧化吲哚类衍生物的绿色方法，其制备过程为：以具有不同官能团的吲哚类化合物为原料，在室温、敞口、中性条件下，采用MBrx(M为Fe2+、Fe3+、Ce3+等)为催化剂，X＝2或3，过氧化氢为唯一氧化剂，原位生成活性溴(RBS)，催化合成氧化吲哚类衍生物。本发明所述方法通过使用MBrx(如FeBr2、CeBr3等)为催化剂，避免了使用昂贵或复杂的催化剂，绿色环保，安全，简单高效，反应条件温和，底物适用范围广，具有较好的应用前景，有望在有机合成、精细化工和制药工业中得到广泛应用。
• Syntheses of Strychnan- and Aspidospermatan-Type Alkaloids. 10. An Enantioselective Synthesis of (−)-Strychnine through the Wieland−Gumlich Aldehyde
  作者：Martin E. Kuehne、Feng Xu

  DOI：10.1021/jo9813989

  日期：1998.12.1

  Condensations of L-tryptophan-derived 2-[(methoxycarbonyl)methyl]-3-[2(S)-(benzyloxycarbonyl)- 2-(N-b-benzylamino)ethyl]indole (6) with 4,4-dimethoxyacrolein or with 2,4-hexadienal, followed by removal of the tryptophanyl ester function, respectively gave the tetracyclic acetal (-)-methyl (2S, 3aS,5R,11bR)-3-benzyl-2,3,3a,4,5,7-hexahydro-5-(dimethoxymethyl)-1H-pyrrolo[2,3-d]carbazole-6-carboxylate (10) or the tetracyclic olefin (-)-methyl (2S,3aS,5R,11bR)-3-benzyl-2,3,3a,4,5,7-hexahydro-5-(1-propenyl)-1H-pyrrolo[2,3-d]carbazole-6-carboxylate (14). Their respective hydrolysis or oxidation provided, enantioselectively, the tetracyclic aldehyde (-)-methyl (2S,3aS,5R,11bR)3-benzyl-2,3,3a,4,5,7-hexahydro-5-formyl-1H-pyrrolo[2,3-d]carbazole-6-carboxylate (5). Its reaction with tri-n-butyl-1-(ethoxy)ethoxymethyltin and n-butyllithium, followed by oxidation of the resultant alcohol (-)-methyl (2S,3aS,5R,11bR)-3-benzyl-2,3,3a,4,5,7-hexahydro-5-(1 xi-hydroxy-2-((1-ethoxy-ethoxy))ethyl-1H-pyrrolo[2,3-d]carbazole-6-carboxylate (16) and cyclization furnished the pentacyclic ketone (-)-methyl (2S,3aS,5R,11bR)-3-benzyl-2,3,3a,4,5,7-hexahydro-3,5-ethano-12-oxo-1H-pyrrolo-2,3-d]carbazole-6-carboxylate (15). A Horner-Emmons condensation led to the unsaturated esters (-)-methyl (2S,3aS,5R,11bR)-3-benzyl-2,3,3a,4,5,7-hexahodro-3,5-ethano-12-(E and Z)-[(methoxycarbonyl)-methylene]-1H-pyrrolo[2,3-d]carbazole-6-carboxylates(19 and 20) with 17:1 E/Z selectivity. Reductions of the ester and vinylogous urethane functions in 19 led to the Wieland-Gumlich aldehyde 3 as a 6:1 anomeric hemiacetal mixture. Its condensation with malonic acid provided (-)-strychnine (1) in 5.3% overall yield and 14 steps from the tryptophan derivative 6.
• Oxazolidinones and 2,5-Dihydrofurans via Zinc-Catalyzed Regioselective Allenylation Reactions of <scp>l</scp>-α-Amino Aldehydes
  作者：Farzad Zamani、Stephen G. Pyne、Christopher J. T. Hyland

  DOI：10.1021/acs.joc.7b00969

  日期：2017.7.7

  The simultaneous control of diastereoselectivity and regioselectivity in Zn-catalyzed allenylation reactions of N-protected L-alpha-amino aldehydes is reported. A reversal in diastereoselectivity could be realized by variation of the alpha-amino aldehyde protecting groups. A range of 1-allenyl-2-amino alcohols were obtained with excellent regioselectivity and converted to oxazolidinones and dihydrofurans. Many of which could be isolated as single diastereoisomers and without significant erosion of ee, making this a practical catalytic synthesis of highly functionalized heterocycles.