3-methyl-2-pyrrol-1-ylbutyric acid methyl ester | 696647-68-4

• 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: 3-methyl-2-pyrrol-1-ylbutyric acid methyl ester
• 英文别名: methyl (2S)-3-methyl-2-pyrrol-1-ylbutanoate
• CAS: 696647-68-4
• 化学式: C₁₀H₁₅NO₂
• mdl: MFCD05257754
• 分子量: 181.235
• InChiKey: HIHWPYKPNOPVBM-VIFPVBQESA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2
• 重原子数：
  13
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  31.2
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  3-methyl-2-pyrrol-1-ylbutyric acid methyl ester 在 三氯氧磷 作用下， 以 二氯甲烷 、 苯 为溶剂， 反应 0.5h， 生成 (2R,3S,6S,10bR)-3-methyl-6-isopropyl-2-phenyl-2,3-dihydro-10bH-[1,3]oxazolo[3,2-a]pyrrolo[2,1-c]pyrazin-5(6H)-one
  参考文献：
  名称：

  Intermolecular one-pot cyclization of formyl-pyrroles of amino acid esters with norephedrine: stereoselective routes to new tricyclic pyrrole–pyrazine–oxazole fused structures

  摘要：

  The treatment of esters of amino acids with dimethoxytetrahydrofuran furnished pyrrole derivatives of amino acid esters. The Wilsmeier-Haack formylation followed by the reaction of the formylated pyrroles with norephedrine afforded a selective formation of the tricyclic pyrrole-pyrazine-oxazole fused structures in one step via the formation of an oxazoline structure and intramolecular lactam formation. Pyrrole-pyrazine-oxazole fused structures were achieved in good yields. The cyclization reaction for the formation of an oxazole ring worked selectively to form only one stereoisomer. The configuration of the newly generated stereogenic center in the oxazole ring is dependent on the stereogenic centers of norephedrine. (c) 2006 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetasy.2006.09.020
• 作为产物：
  描述：

  顺式-1,4-二氯-2-丁烯 、 L-缬氨酸甲酯 在 air 、 silica gel 、 三乙胺 作用下， 反应 0.03h， 以51%的产率得到3-methyl-2-pyrrol-1-ylbutyric acid methyl ester
  参考文献：
  名称：

  New and clean synthesis of N-substituted pyrroles under microwave irradiation

  摘要：

  N-Substituted homochiral pyrrole derivatives were synthesized by the ring-closure reaction of cis-1,4-dichloro-2-butene with various amine compounds on a silica surface under microwave irradiation. (c) 2007 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tet.2007.07.013

文献信息

• Crucial Role of β-Elimination in Determining Regio- and Chemoselectivity of the Rhodium-Catalyzed Hydroformylation of N-Allylpyrroles: A New Approach to 5,6-Dihydroindolizines
  作者：Roberta Settambolo

  DOI：10.1055/s-0030-1257860

  日期：2010.9

  Rhodium-catalyzed hydroformylation of the chiral (S)-3-alkyl-3-pyrrol-1-ylprop-1-enes at 100 atmospheres total pressure and 25 ˚C led to the preferential formation of the branched 3-alkyl-2-methyl-3-pyrrol-1-ylpropanals. At 30 atmospheres and 125 ˚C, the linear 4-alkyl-4-pyrrol-1-ylbutanals were obtained: these aldehydes are not the final products, but evolve into more stable 5,6-dihydroindolizines, with the same optical purity as the starting olefins, via a domino cyclization-dehydration process. According to the generally accepted mechanism for rhodium-catalyzed hydroformylation, the regioselectivity, and then the final chemoselectivity, can be rationalized by taking into account that while at room temperature no β-elimination occurs, at high temperature the β-elimination involves the branched rhodium-alkyl intermediate only.

  铑催化的手性 (S)-3-烷基-3-吡咯-1-基丙-1-烯在100大气压和25°C下反应，优先生成支链的 3-烷基-2-甲基-3-吡咯-1-基丙醛。在30大气压和125°C时，得到线性 4-烷基-4-吡咯-1-基丁醛：这些醛类不是最终产物，而是通过多米诺环化-脱水过程演变为更稳定的 5,6-二氢吲哚啉，且与起始烯烃具有相同的光学纯度。根据普遍接受的铑催化加氢反应机制，可以合理解释区域选择性以及最终的化学选择性，因为在常温下没有发生β-消除，而在高温下，β-消除仅涉及支链铑-烷基中间体。
• Discrimination of Enantiofaces and Stereoselective Electrophilic Addition Reactions for η²-Pyrrole Complexes
  作者：Mark T. Valahovic、William H. Myers、W. Dean Harman

  DOI：10.1021/om020606r

  日期：2002.10.1

  coordination diastereomer according to their NMR spectra (−5 to −20 °C). This stereoselective coordination results in stereoselective electrophilic addition at the uncoordinated β carbon (C3) when the complexes are treated with trifluoromethanesulfonic acid (HOTf), methyl triflate, or dimethoxymethane. These stereoselective reactions at C3 are a direct result of differentiation of the pyrrole enantiofaces

  一系列的不对称ñ -取代吡咯（1 - 7）已经从氨基酸衍生物合成和络合到pentaammineosmium（II）片段。许多这些吡咯络合物（的8 - 14）示出了用于一个非对映体协调热力学优选根据它们的NMR谱（-5至-20℃）。当用三氟甲烷磺酸（HOTf），三氟甲磺酸甲酯或二甲氧基甲烷处理络合物时，这种立体选择性配位导致在未配位的β碳（C3）处发生立体选择性亲电子加成。在C3处的这些立体选择性反应是吡咯对映体分化的直接结果。
• Arylation of Cyclopropanol with Pyrrole: Asymmetric Synthesis of Indolizidine 167B, Indolizidine 209D, and Monomorine I
  作者：Shuangwei Liu、Xiaojiao Su、Dan Jiang、Hongbing Xiong、Dingyin Miao、Lin Fu、Hanyue Qiu、Ling He、Min Zhang

  DOI：10.1021/acs.orglett.3c00406

  日期：2023.3.31

  and thus allows rapid access to a diverse array of chiral 5,6,7,8-tetrahydroindolizines from easily available chiral amino acid esters. The synthetic utility has been demonstrated by the asymmetric synthesis of alklaoids (−)-indolizidine 167B, (+)-indolizidine 209D, (+)-monomorine I, and a natural product analogue.

  已开发出Fe(NO 3 ) 3介导的环丙醇与富电子吡咯的开环芳基化反应，该反应可能通过环丙醇的氧化自由基开环，然后环化为吡咯基序，然后芳构化进行。该方法无需预官能化即可实现环丙醇的直接芳基化，因此可以从易于获得的手性氨基酸酯中快速获得各种手性 5,6,7,8-四氢二氢吲嗪。合成效用已通过生物碱 (−)-indolizidine 167B、(+)-indolizidine 209D、(+)-monomorine I 和天然产物类似物的不对称合成得到证明。
• Kashima, Choji; Maruyama, Tatsuya; Harada, Kazuo, Journal of Chemical Research, Miniprint, 1988, # 2, p. 601 - 645
  作者：Kashima, Choji、Maruyama, Tatsuya、Harada, Kazuo、Hibi, Shigeki、Omote, Yoshimori

  DOI：——

  日期：——
• Intermolecular one-pot cyclization of formyl-pyrroles of amino acid esters with norephedrine: stereoselective routes to new tricyclic pyrrole–pyrazine–oxazole fused structures
  作者：Ayhan S. Demir、N. Tuna Subasi、Ertan Sahin

  DOI：10.1016/j.tetasy.2006.09.020

  日期：2006.10

  The treatment of esters of amino acids with dimethoxytetrahydrofuran furnished pyrrole derivatives of amino acid esters. The Wilsmeier-Haack formylation followed by the reaction of the formylated pyrroles with norephedrine afforded a selective formation of the tricyclic pyrrole-pyrazine-oxazole fused structures in one step via the formation of an oxazoline structure and intramolecular lactam formation. Pyrrole-pyrazine-oxazole fused structures were achieved in good yields. The cyclization reaction for the formation of an oxazole ring worked selectively to form only one stereoisomer. The configuration of the newly generated stereogenic center in the oxazole ring is dependent on the stereogenic centers of norephedrine. (c) 2006 Elsevier Ltd. All rights reserved.