(4S)-4-(N-叔丁氧羰基)氨基-5-苯基-2-戊烯-1-醇 | 124818-93-5

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 中文名称: (4S)-4-(N-叔丁氧羰基)氨基-5-苯基-2-戊烯-1-醇
• 英文名称: (4S)-4-(N-tert-butoxycarbonyl)amino-5-phenyl-2-penten-1-ol
• 英文别名: tert-Butyl (2E)-1-benzyl-4-hydroxy-2-butenylcarbamate；tert-butyl N-[(E,2S)-5-hydroxy-1-phenylpent-3-en-2-yl]carbamate
• CAS: 124818-93-5
• 化学式: C₁₆H₂₃NO₃
• 分子量: 277.364
• InChiKey: LDGKQMWUFPKKRJ-DNGMOHDESA-N

物化性质

• 沸点：
  426.5±45.0 °C(Predicted)
• 密度：
  1.074±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.5
• 重原子数：
  20
• 可旋转键数：
  7
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.44
• 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：

  (4S)-4-(N-叔丁氧羰基)氨基-5-苯基-2-戊烯-1-醇 在 吡啶 、 盐酸 、 四(三苯基膦)钯 、 potassium carbonate 作用下， 以 二氯甲烷 、 水 、 乙酸乙酯 、 乙腈 为溶剂， 反应 38.5h， 生成 (4S-trans)-4,5-dihydro-4-benzyl-2-phenyl-5-vinyloxazoline
  参考文献：
  名称：

  Stereoselective Intramolecular Cyclization of Allyl and Homoallyl Benzamide via π-Allylpalladium Complex Catalyzed by Pd(0)

  摘要：

  The transformation of acyclic allylic benzamides 4 and homoallylic benzamides 12 to vinyl oxazolines 3 is achieved in the presence of base by the catalysis of Pd(0) in high yield and with high diastereoselectivity. Especially, in the case of homoallylic benzamides 12, trans-oxazolines 3 are formed exclusively or predominantly over cis-oxazolines 8, irrespective of the composition of their stereoisomers. The reaction is believed to proceed via the same pi-allylpalladium complex that arises from either primary or secondary allylic acetates. We applied this method to the syntheses of beta-amino-alpha-hydroxy acids 1 and gamma-amino-beta-hydroxy acids 2, conveniently protected as oxazoline.

  DOI：

  10.1021/jo991065r
• 作为产物：
  描述：

  BOC-PHE-甲氧基甲胺 在 lithium aluminium tetrahydride 、 三氟化硼乙醚 、 sodium hydride 、 二异丁基氢化铝 作用下， 以 四氢呋喃 、 二氯甲烷 为溶剂， 生成 (4S)-4-(N-叔丁氧羰基)氨基-5-苯基-2-戊烯-1-醇
  参考文献：
  名称：

  Irreversible inhibitions of serine proteases by peptidyl allylic halide derivatives

  摘要：

  Peptidyl 4-amino-5-phenyl-2-pentenyl bromide (7a, 9a, 10a) and chloride derivatives (7b, 9b, 10b) were found to be active-site directed irreversible inhibitors of alpha-chymotrypsin but did not show any irreversible inhibitory activity toward porcine pancreatic elastase.

  DOI：

  10.1016/0960-894x(95)00592-h

文献信息

• Hydrogen Bond Directed Highly Regioselective Palladium-Catalyzed Allylic Substitution
  作者：Gregory R. Cook、Hui Yu、S. Sankaranarayanan、P. Sathya Shanker

  DOI：10.1021/ja028426w

  日期：2003.4.1

  The palladium-catalyzed allylic substitution of 5-vinyloxazolidinones and derivatives was investigated. Unusual and high regioselectivity for the branched product was observed. The regioselectivity was influenced by the type of substrate, the solvents, and the nucleophile. Imide-type nucleophiles were found to be directed to the internal carbon (branched:linear, 75:25 to >98:2), whereas sulfonamides

  研究了钯催化的 5-乙烯基恶唑烷酮和衍生物的烯丙基取代。观察到支化产物的异常和高区域选择性。区域选择性受底物类型、溶剂和亲核试剂的影响。发现酰亚胺型亲核试剂指向内部碳（支链：线性，75:25 至 >98:2），而磺酰胺、胺和丙二酸酯仅添加到烯丙基复合物的末端碳。相对非极性的溶剂如甲苯和四氢呋喃有利于支化产物（分别为 97:3 和 95:5）。乙腈和二氯甲烷提供较低的区域选择性（分别为 50:50 和 67:33），而质子溶剂乙醇的使用导致区域选择性的逆转（12:88）。基板上的导向组很重要。酰胺几乎完全形成支化产物，氨基甲酸酯得到区域异构体的 50:50 混合物，邻苯二甲酰亚胺作为亲核试剂。亲核试剂通过氢键定向的证据是通过用甲基取代酰胺的氢获得的，导致仅产生正常的线性产物。
• Highly Stereoselective Intramolecular S_N2′ Cyclization Yielding Chiral ­Oxazolidin-2-ones: General Route to α-Hydroxy-β-amino Acids
  作者：Ki Hun Park、Woo Duck Seo、Marcus J. Curtis-Long、Jin Hyo Kim、Jong Keun Park、Ki Min Park

  DOI：10.1055/s-2005-872264

  日期：——

  Intramolecular nucleophilic attack onto allylsulfonates promoted by silica gel acting as an acid catalyst provides expedient stereoselective access to 4,5-difunctionalized oxazolidin-2-ones. Precursors were prepared efficiently from enantiopure α-amino acids and subsequent manipulation of the oxazolidin-2-ones yielded enantiopure α-hydroxy-β-amino acids.

  硅胶作为酸催化剂促进对烯丙基磺酸盐的分子内亲核攻击提供了对 4,5-双官能化 2-酮的立体选择性访问。前体是由对映纯的 α-氨基酸有效制备的，随后对恶唑烷-2-酮的操作产生了对映纯的 α-羟基-β-氨基酸。
• A new mode of cyclic carbamate formation via tert-butyldimethylsilyl carbamate. Stereoselective syntheses of statine and its analogue
  作者：Masahiro Sakaitani、Yasufumi Ohfune

  DOI：10.1016/s0040-4039(00)96439-6

  日期：1987.1

  Stereoselective construction of 1,2- and 1,3-amino hydroxyl systems was carried out using SN2′ (initiated by AgF or AgF-Pd(II)) cyclic carbamate formations from tert-butyldimethyl silyl carbamates. This method was applied to the syntheses of statine and AHPPA, efficiently.

  使用S N 2'（由AgF或AgF-Pd（II）引发）由叔丁基二甲基甲硅烷基氨基甲酸酯形成的环状氨基甲酸酯，进行1,2-和1,3-氨基羟基系统的立体选择性构建。该方法有效地应用于了他汀类药物和AHPPA的合成。
• Stereoselective syntheses of α-hydroxy-γ-amino acids: possible γ-turn mimetics
  作者：Manfred T. Reetz、Nils Griebenow、Richard Goddard

  DOI：10.1039/c39950001605

  日期：——

  Enantiomerically pure 4-amino-allyloxy-acetates, prepared from L-amino acids, undergo a Stereoselective Wittig rearrangements with formation of the corresponding α-hydroxy-γ-amino acid esters having γ-turn conformational features.

  由L-氨基酸制备的对映体纯的4-氨基-烯丙氧基乙酸酯经历立体选择性维蒂希重排，形成具有γ-转角构象特征的相应α-羟基-γ-氨基酸酯。
• Asymmetric induction in a new domino reaction of [3,3]-sigmatropic rearrangement of allylic thiocyanates and intramolecular heterocyclisation
  作者：Jozef Gonda、Miroslava Martinková、Ján Imrich

  DOI：10.1016/s0040-4020(02)00026-1

  日期：2002.2

  route to diastereomerically pure (4S,5S)-4-vinyltetrahydro-1H-2-imidazolethiones via a novel domino reaction of [3,3]-sigmatropic rearrangement of chiral thiocyanates followed by stereoselective intramolecular amine addition to arising isothiocyanates is reported.

  一种新的合成途径，通过手性硫氰酸酯的[3,3]-σ重排的新多米诺反应，然后向立体异构体中添加非立体异构纯的（4 S，5 S）-4-乙烯基四氢-1 H -2-咪唑硫酮据报道有异硫氰酸酯。