methyl (4S,2Z)-2-benzyloxycarbonylamino-4,5-isopropylidenedioxy-2-pentanoate | 132970-32-2

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: methyl (4S,2Z)-2-benzyloxycarbonylamino-4,5-isopropylidenedioxy-2-pentanoate
• 英文别名: methyl (Z)-3-[(4S)-2,2-dimethyl-1,3-dioxolan-4-yl]-2-(phenylmethoxycarbonylamino)prop-2-enoate
• CAS: 132970-32-2
• 化学式: C₁₇H₂₁NO₆
• 分子量: 335.357
• InChiKey: FZAMSMJPEPEIMJ-GFAPJHNFSA-N

物化性质

• 沸点：
  471.4±45.0 °C(predicted)
• 密度：
  1.237±0.06 g/cm3(Temp: 20 °C; Press: 760 Torr)(predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.9
• 重原子数：
  24
• 可旋转键数：
  7
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.41
• 拓扑面积：
  83.1
• 氢给体数：
  1
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  methyl (4S,2Z)-2-benzyloxycarbonylamino-4,5-isopropylidenedioxy-2-pentanoate 在 palladium dihydroxide 1,3-二甲基-2-苯基-2-磷杂咪唑烷 、 盐酸 、 甲醇 、 sodium hydroxide 、 二苯甲酮 、 氢气 作用下， 以 四氢呋喃 、 甲醇 、 乙醚 、 二氯甲烷 为溶剂， -78.0~40.0 ℃ 、101.33 kPa 条件下， 反应 81.3h， 生成 (1S,2R)-1-氨基-2-乙基环丙烷羧酸
  参考文献：
  名称：

  Enantioselective total syntheses of cyclopropane amino acids: Natural products and protein methanologs

  摘要：

  The syntheses of (-)-allo-coronamic acid, (-)-allo-norcoronamic acid, (-)-(Z)-2, 3-methanohomoserine, (-)-(Z)-2, 3-methanomethionine, and (2S, 3R)-Cbz-cyclo-Asp-OMe have been achieved in 45-68% overall yields from suitable intermediates derived from homochiral aminopentenoates which were obtained, in bun, from D-glyceraldehyde. The key synthetic step involves the quantitative and highly diastereoselective cyclopropanation of such precursors. The factors dealing with the control of stereoselectivity are highlighted and the main features in sidechain functionalization to the respective target molecules are discussed.

  DOI：

  10.1016/0957-4166(96)00038-9
• 作为产物：
  描述：

  (±)-Z-α-膦酰甘氨酸三甲酯 、 (R)-(+)-2,2-二甲基-1,3-二氧戊环-4-甲醛 在 potassium tert-butylate 作用下， 以85%的产率得到methyl (4S,2Z)-2-benzyloxycarbonylamino-4,5-isopropylidenedioxy-2-pentanoate
  参考文献：
  名称：

  Enantioselective total syntheses of cyclopropane amino acids: Natural products and protein methanologs

  摘要：

  The syntheses of (-)-allo-coronamic acid, (-)-allo-norcoronamic acid, (-)-(Z)-2, 3-methanohomoserine, (-)-(Z)-2, 3-methanomethionine, and (2S, 3R)-Cbz-cyclo-Asp-OMe have been achieved in 45-68% overall yields from suitable intermediates derived from homochiral aminopentenoates which were obtained, in bun, from D-glyceraldehyde. The key synthetic step involves the quantitative and highly diastereoselective cyclopropanation of such precursors. The factors dealing with the control of stereoselectivity are highlighted and the main features in sidechain functionalization to the respective target molecules are discussed.

  DOI：

  10.1016/0957-4166(96)00038-9

文献信息

• Stereoselective Synthesis of (<i>E</i>)-α,β-Dehydroamino Acid Esters
  作者：Yoko Yasuno、Makoto Hamada、Takeshi Yamada、Tetsuro Shinada、Yasufumi Ohfune

  DOI：10.1002/ejoc.201300112

  日期：2013.4

  Dehydroamino acid (Dhaa) is recognized as a useful tool or substrate for amino acid and peptide research. Although the stereoselective synthesis of the thermodynamically more stable Z-Dhaa has been well examined and established, the stereoselective synthesis of E-Dhaa has still remained to be a challenging synthetic task. In this paper, a stereoselective synthesis of E-Dhaa esters using a new (α-d

  脱氢氨基酸 (Dhaa) 被认为是氨基酸和肽研究的有用工具或底物。尽管热力学上更稳定的 Z-Dhaa 的立体选择性合成已得到充分研究和确立，但 E-Dhaa 的立体选择性合成仍然是一项具有挑战性的合成任务。在本文中，描述了使用新的（α-二苯基膦酰基）甘氨酸立体选择性合成 E-Dhaa 酯。新方法的特征方面总结如下：（i）金属添加剂在促进 E 立体选择性方面起着重要作用。(ii) NaI 用于合成带有芳基取代基和氨基官能团的 E-Dhaas，
• Syntheses of 2-[(1<i>S</i>,3<i>S</i>)-1-Amino-3-carboxy-3-hydroxypropyl]thiazole-4-carboxylic Acid and the Tripeptide Skeleton of Nosiheptide Containing the Acid
  作者：Chung-gi Shin、Yutaka Nakamura、Yasuhiro Yamada、Yasuchika Yonezawa、Kazuyuki Umemura、Juji Yoshimura

  DOI：10.1246/bcsj.68.3151

  日期：1995.11

  The stereoselective synthesis of an amino acid component called Fragment D, N,O-diprotected 2-[(1S,3S)-1-amino-3-carboxy-3-hydroxypropyl]thiazole-4-carboxylic acid of a macrobicyclic peptide antibiotic nosiheptide, was achieved by two routes. The dipeptide, Fragment B-C, 2-[(Z)-1-(N,O-isopropylidene-L-threonylamino)-1-propenyl]thiazole-4-carboxylic acid was also synthesized by the thiazole ring formation

  一种氨基酸成分的立体选择性合成，称为片段 D，N，O-diprotected 2-[(1S,3S)-1-amino-3-carboxy-3-hydroxypropyl]thiazole-4-羧酸的大双环肽抗生素那西肽，是通过两条路线实现的。二肽，片段 BC，2-[(Z)-1-(N,O-isopropylidene-L-threonylamino)-1-propenyl]thiazole-4-羧酸也通过 (Z)-的噻唑环形成合成2-(N,O-双保护的 L-苏氨酰氨基)-2-丁烯硫酰胺与溴丙酮酸乙酯。通过使用缩合剂将两个组分偶联得到预期的三肽 2，它是那西肽的重要部分骨架。
• Amino Acids and Peptides; 75. Synthesis of Di- and Trihydroxyamino Acids - Construction of Lipophilic Tripalmitoyldihydroxy-α-amino Acids
  作者：Ulrich Schmidt、Albrecht Lieberknecht、Uli Kazmaier、Helmut Griesser、Günther Jung、Jörg Metzger

  DOI：10.1055/s-1991-26378

  日期：——

  Suitable protected derivatives of trihydroxynorleucines-[(2S,4S,5S)- and (2R,4S,5S)-2-amino-4,5,6-trihydroxyhexanoic acid,] of all isomeric dihydroxynorvalines [2-amino-4,5-dihydroxypentanoic acids), of all isomeric 2-amino-6,7-dihydroxyheptanoic acids and of (2S)-2-amino-6-hydroxymethyl-7-hydroxyheptanoic acid are synthesized via the corresponding α,β-didehydro compounds, which are hydrogenated with the optically active homogeneous catalyst [Rh(COD)(DIPAMP)]+ BF- 4.

  (2S,4S,5S)-和(2R,4S,5S)-2-氨基-4,5,6-三羟基己酸、]所有异构体二羟基缬氨酸[2-氨基-4,5-二羟基戊酸]、所有异构体2-氨基-6、7-二羟基庚酸和 (2S)-2- 氨基-6-羟甲基-7-羟基庚酸是通过相应的 δ、δ²-二氢化物合成的，这些化合物在光学活性均相催化剂[Rh(COD)(DIPAMP)]+ BF- 4 的作用下进行氢化。
• 1,3-Dipolar Cycloadditions of Diazomethane to Chiral Electron-Deficient Olefins:  The Origin of the π-Facial Diastereoselection
  作者：Elena Muray、Angel Alvarez-Larena、Joan F. Piniella、Vicenç Branchadell、Rosa M. Ortuño

  DOI：10.1021/jo991227j

  日期：2000.1.1

  The stereochemical outcome of diazomethane cycloadditions to several chiral electron-deficient olefins has been investigated in order to establish the origin of the pi-facial diastereoselection. Nitro olefins, vinyl sulfones, enoates, and 2-amino enoates have been used for such a purpose. These substrates have been prepared from D-glyceraldehyde acetonide through Wittig-type condensations and present

  研究了重氮甲烷环加成到几种手性电子缺陷烯烃上的立体化学结果，以便确定pi非对映选择性的起源。硝基烯烃，乙烯基砜，烯酸酯和2-氨基烯酸酯已用于此目的。这些底物是由D-甘油醛丙酮化物通过Wittig型缩合反应制得的，并具有一个由庞大的二氧戊环提供的烷氧基取代基，该取代基与立体异构的烯丙基碳相连。在所有情况下，均已获得作为主要异构体的加合物，而与双键的Z / E立体化学以及取代基的数量和性质无关，不对称烯丙基碳的手性是造成非对映异构的唯一原因。
• Highly efficient and stereocontrolled synthetic route to enantiopure ACC derivatives
  作者：José M. Jiménez、Ramon Casas、Rosa M. Ortuño

  DOI：10.1016/s0040-4039(00)78226-8

  日期：1994.8

  Highly diastereoselective cyclopropanation of a chiral α,β-dehydroamino acid derivative, obtained from D-mannitol, leads to a single isomer which has been transformed into the title compound in 65% overall yield. This product can be a useful intermediate in the synthesis of enantiopure ACC derivatives.

  由D-甘露糖醇获得的手性α，β-脱氢氨基酸衍生物的高度非对映选择性环丙烷化产生单一异构体，该异构体以65％的总收率转化为标题化合物。该产物可能是合成对映纯ACC衍生物的有用中间体。