(+/-)-(1-hydroxymethallyl)carbamic acid benzyl ester | 186759-45-5

• 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: (+/-)-(1-hydroxymethallyl)carbamic acid benzyl ester
• 英文别名: (S)-N-benzyloxycarbonyl-2-amino-3-butenol；(SR)-N-Benzyloxycarbonylvinylglycinol；N-Cbz vinyl glycinol；2-(N-benzyloxycarbonylamino)-3-buten-1-ol；2-benzyloxycarbonylamino-but-3-en-1-ol；Benzyl N-(1-hydroxybut-3-en-2-yl)carbamate
• CAS: 186759-45-5
• 化学式: C₁₂H₁₅NO₃
• 分子量: 221.256
• InChiKey: JQUKUTGUTGNLHF-UHFFFAOYSA-N

物化性质

• 沸点：
  399.1±42.0 °C(Predicted)
• 密度：
  1.143±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.4
• 重原子数：
  16
• 可旋转键数：
  6
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.25
• 拓扑面积：
  58.6
• 氢给体数：
  2
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  (+/-)-(1-hydroxymethallyl)carbamic acid benzyl ester 在 palladium diacetate 、 铁粉 、 溶剂黄146 、 三苯基膦 、 silver carbonate 、 偶氮二甲酸二乙酯 作用下， 以 乙醇 、 二氯甲烷 、 水 、 甲苯 、 乙腈 为溶剂， 反应 32.0h， 生成 3-benzyloxycarbonylamino-4-methylen-5-trifluoroacetamide-chromane
  参考文献：
  名称：

  An innovative strategy for the synthesis of a new series of potent aminopeptidase (APN or CD13) inhibitors derived from the oxepin-4-one family

  摘要：

  Derivatives from the aminobenzosuberone family have been recently synthesized and recognized as highly selective inhibitors of aminopeptidase N (APN)/CD13 (EC 3.4.11.2), an important target for cell migration processes involved in particular in tumor invasion. We present here a much more straightforward synthesis of analogues belonging to a novel isosteric oxo series which also possesses excellent inhibitory potential against APN. Their synthesis, as reported here, relied on an interesting iodine(III)-mediated rearrangement originally described by Koser and Justik as the key step. This represents the second application of this rearrangement in medicinal chemistry. (C) 2011 Published by Elsevier Ltd.

  DOI：

  10.1016/j.tetlet.2011.03.043
• 作为产物：
  描述：

  hydroxymethyl carbamic acid benzyl ester 在 吡啶 、 盐酸 、 sodium benzoate 、 palladium(II) trifluoroacetate 、 氧气 、 4-甲基苯磺酸吡啶 、 二甲基亚砜 作用下， 以 四氢呋喃 、 乙醇 、 二氯甲烷 、 水 为溶剂， 20.0~85.0 ℃ 、101.33 kPa 条件下， 反应 33.22h， 生成 (+/-)-(1-hydroxymethallyl)carbamic acid benzyl ester
  参考文献：
  名称：

  通过立体选择性 Aza-Wacker 环化合成邻位氨基醇：通过氧化还原继电器获得 (−)-Acosamine

  摘要：

  O-烯丙基半缩醛胺在有氧条件下的非对映选择性氮杂-瓦克环化能够有效地从烯丙醇获得1,2-氨基醇衍生物。介绍了该方法的范围，并在生物学上重要的氨基糖 (−)-阿科胺的简化合成中强调了其实用性。 Cbz=苄氧基羰基，TBDPS=叔丁基二苯基甲硅烷基，TBS=叔丁基二甲基甲硅烷基。

  DOI：

  10.1002/anie.201305926

文献信息

• 2-(3-Pyrrolin-1-yl)-1,4-naphthoquinones: Photoactivated Alkylating Agents
  作者：Aaron Aponick、Amber L. Dietz、William H. Pearson

  DOI：10.1002/ejoc.200800482

  日期：2008.9

  The preparation of 2-(3-pyrrolin-1-yl)-1,4-naphthoquinones and a study of their use as photoactivated alkylating agents is reported. The title compounds were easily synthesized by conjugate addition of the corresponding 3-pyrrolines to various naphthoquinones. Upon exposure to ambient room light, the compounds undergo an internal redox reaction to form 2-(pyrrol-1-yl)-1,4-hydroquinones, which are activated

  报道了 2-(3-pyrrolin-1-yl)-1,4-naphthoquinones 的制备及其作为光活化烷化剂的用途。通过将相应的 3-吡咯啉与各种萘醌进行共轭加成，很容易合成标题化合物。暴露于环境室内光线后，这些化合物会发生内部氧化还原反应，形成 2-(pyrrol-1-yl)-1,4-hydroquinone，其被活化为
• Synthesis of Unnatural Amino Acids via Suzuki Cross-Coupling of Enantiopure Vinyloxazolidine Derivatives
  作者：Mark Sabat、Carl R. Johnson

  DOI：10.1021/ol005645i

  日期：2000.4.1

  S)-alpha-Amino alcohols and alpha-amino acids, including 4-methoxyhomophenylalanine, with a variety of unnatural side chains have been synthesized via palladium-catalyzed cross-coupling Suzuki reactions. The key building blocks 1 and 2, synthesized from the common achiral precursor 2-butene-1,4-diol, were made enantiopure utilizing a Pseudomonas cepacia lipase-catalyzed kinetic resolution. The optimal

  通过钯催化的交叉偶联Suzuki反应合成了（R和S）-α-氨基醇和α-氨基酸，包括4-甲氧基高苯丙氨酸，并带有各种非天然的侧链。由常见的非手性前体2-丁烯-1,4-二醇合成的关键结构单元1和2，利用假单胞菌洋葱脂肪酶催化的动力学拆分，制成对映体纯净的。描述了铃木交叉偶联和随后氧化所得α-氨基醇的最佳条件。
• The Stereoselective Synthesis of 2-Substituted 3-Azabicyclo[3.2.0]heptanes by Intramolecular [2+2]-Photocycloaddition Reactions
  作者：Thorsten Bach、Christa Krüger、Klaus Harms

  DOI：10.1055/s-2000-6261

  日期：——

  The stereoselective synthesis of the 3-azabicyclo[3.2.0]heptanes 6, 12, 13, 17, 22, 23 and 24 by an intramolecular [2+2]-photocycloaddition is described. The product yield was good to excellent in almost all cases studied (65-87%) except for a single example (21 → 24) in which a low yield was recorded (22%). The facial diastereoselectivity of the reaction is high if α-branched N,N-diallylamines are employed as starting materials which either bear a comparably bulky α-substituent (25) or the α-substituent of which is connected to the nitrogen atom via an oxazolidinone ring (16, 19, 20, 21). These diallylamines were readily prepared from methionine and it was shown that their preparation proceeded free of racemization. The photocycloaddition could be conducted in two ways. The more general method is based on the Cu-catalyzed reaction which was carried out with Cu(OTf)2 in diethyl ether and is applicable to essentially all substrates under scrutiny. The N-cinnamyl substituted substrates 5, 11, 16 and 25 which possess a comparably low lying T1 state reacted well in a triplet-sensitized process employing acetophenone as the sensitizer and acetone as the solvent.

  本文描述了通过分子内[2+2]光环加成反应合成3-氮杂双环[3.2.0]庚烷6、12、13、17、22、23和24的手性选择性合成方法。在所有研究的情况中，产物收率良好至优异（65-87%），仅有一个例外（21→24）记录到较低的收率（22%）。如果使用α-支链的N,N-二烯丙基胺作为起始材料，这些材料要么带有相对较大的α-取代基（25），要么其α-取代基通过恶唑烷酮环与氮原子相连（16、19、20、21），反应的面选择性非常高。这些二烯丙基胺很容易从甲硫氨酸制备，并且证明其制备过程没有发生消旋化。光环加成反应可以通过两种方式进行。更通用的方法是基于铜催化的反应，使用Cu(OTf)2在二乙醚中进行，适用于几乎所有待研究的底物。拥有相对较低T1态的N-肉桂基取代底物5、11、16和25在三重态敏化过程中反应良好，使用乙酰苯作为敏化剂，丙酮作为溶剂。
• Asymmetric cyclization of 2-butenylene dicarbamates catalyzed by chiral ferrocenylphosphine-palladium complexes: Catalytic asymmetric synthesis of optically active 2-amino-3-butenols
  作者：Tamio Hayashi、Akihiro Yamamoto、Yoshihiko Ito

  DOI：10.1016/0040-4039(88)80027-3

  日期：1988.1

  Cyclization of 2-butenylene dicarbamates (RNHCOOCH2CH=CHCH2OCONHR: R = Ph, MeOC6H4, PhCHCH, etc.) in the presence of a palladium catalyst coordinated with chiral (hydroxyalkyl)-ferrocenylphosphine ligand gave optically active 4-vinyl-2-oxazolidones (up to 77% ee) in high yields, which were hydrolyzed to optically active 2-amino-3-butenols.

  在手性（羟烷基）-二茂铁基膦配体配位的钯催化剂存在下，将2-丁烯二氨基甲酸酯（RNHCOOCH 2 CH = CHCH 2 OCONHR：R = Ph，MeOC 6 H 4，PhCHCH等）环化，得到旋光的4-高产率的乙烯基-2-恶唑烷酮（ee高达77％），将其水解为光学活性的2-氨基-3-丁烯醇。
• A novel approach to azasugars from vinyl glycine methyl ester via olefin metathesis
  作者：Christoph M. Huwe、Siegfried Blechert

  DOI：10.1016/0040-4039(94)02308-x

  日期：1995.3

  A novel strategy for the synthesis of azasugars from vinyl glycine methyl ester was designed, using an olefin metathesis as a key step. As a first test of this strategy, rac-trans-2-hydroxymethyl-3-hydroxypyrrolidine, which was isolated as the (2R,3S)-isomer from the legume Castanospermum australe, was synthesized.

  设计了一种从乙烯基甘氨酸甲酯合成氮杂糖的新策略，该方法以烯烃复分解为关键步骤。作为这种策略，第一测试外消旋-反式-2-羟甲基-3-羟基吡咯烷，将其分离为（2 - [R，3小号从豆科-异构体）Castanospermum AUSTRALE，合成。