tert-butyl (R)-4-[(R)-1-hydroxybut-3-enyl]-2,2-dimethyloxazolidine-3-carboxylate | 220317-59-9

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 唑烷类
• 英文名称: tert-butyl (R)-4-[(R)-1-hydroxybut-3-enyl]-2,2-dimethyloxazolidine-3-carboxylate
• 英文别名: tert-butyl (4S,1'S)-2,2-dimethyl-4-(1'-hydroxy-3'-butenyl)-oxazolidine-3-carboxylate；tert-butyl (4S)-4-(1-hydroxybut-3-enyl)-2,2-dimethyl-1,3-oxazolidine-3-carboxylate
• CAS: 220317-59-9
• 化学式: C₁₄H₂₅NO₄
• 分子量: 271.357
• InChiKey: VRBRTZBCXSQOAT-VUWPPUDQSA-N

物化性质

• 沸点：
  359.8±32.0 °C(Predicted)
• 密度：
  1.053±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2
• 重原子数：
  19
• 可旋转键数：
  5
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.79
• 拓扑面积：
  59
• 氢给体数：
  1
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  tert-butyl (R)-4-[(R)-1-hydroxybut-3-enyl]-2,2-dimethyloxazolidine-3-carboxylate 在 咪唑 、 草酰氯 、 18-冠醚-6 、 cerium(III) chloride heptahydrate 、 dimethyl sulfide borane 、 四丁基氟化铵 、 O,O'-双(2,2,2-三氟乙基)磷乙酸甲酯 、 四丁基碘化铵 、 双(三甲基硅烷基)氨基钾 、 sodium hydride 、 戴斯-马丁氧化剂 、 三乙胺 作用下， 以 四氢呋喃 、 二氯甲烷 、 乙腈 为溶剂， 反应 56.0h， 生成 (2S,3R)-N-tert-butoxycarbonyl-3-benzyloxy-2-[(1'Z)-2'-methoxycarbonylvinyl]piperidine
  参考文献：
  名称：

  从加纳的醛立体选择性形式全合成（-）-Swainsonine

  摘要：

  已经报道了从加纳的1-丝氨酸衍生的恶唑烷醛开始的简单且容易的立体选择性正式全合成（-）-swainsonine 。我们的合成策略涉及立体选择性烯丙基化和Still烯化反应作为关键的中间反应步骤。 swainsonine-铟-烯丙基化-加纳醛-仍然烯烃化-吲哚并立生物碱

  DOI：

  10.1055/s-0030-1258418
• 作为产物：
  描述：

  diisopropyl (S,S)-tartrate allylboronate 、 1,1-二甲基-(r,s)-4-甲酰基-2,2-二甲基-3-噁唑啉羧酸乙酯 在 4 A molecular sieve 作用下， 以 甲苯 为溶剂， 反应 20.0h， 以84%的产率得到tert-butyl (R)-4-[(R)-1-hydroxybut-3-enyl]-2,2-dimethyloxazolidine-3-carboxylate
  参考文献：
  名称：

  Asymmetric Allylboration of 2-N,3-O-Isopropylidene-N-Boc-L-serinal: Diastereoselective Synthesis of the Calicheamicin .gamma.1I Amino Sugar

  摘要：

  Syntheses of the calicheamicin amino sugar 6 and its erythro diastereomer 7 have been completed by a sequence involving the asymmetric allylboration of N-Boc-serinal acetonide L-8 with the tartrate ester modified allylboronates (R,R)-9 and (S,S)-9, respectively. The reaction of(R,R)-9 and L-8 in toluene provides 14 with 89:11 selectivity, whereas the reaction of(S,S)-9 with L-8 in Et(2)O provides the diastereomer 15 with 90:10 selectivity. It is shown that the relatively modest diastereoselectivity of these double asymmetric reactions is compromised by the low enantiomeric purity of 8 (86-87% ee), and data are provided indicating that these reactions should be highly diastereoselective (greater than or equal to 95:5 in each case) if performed with enantiomerically pure aldehyde. The two diastereomeric homoallylic alcohols, 14 and 15, are easily elaborated into the targeted amino sugars 6 and 7 via the acetamide-substituted pyranosides 22 and 26. Methyl pyranosides 22a and 22e were shown to adopt preferentially the unexpected conformations B and D, with axial acetamide substituents, in nonpolar solvents, while the expected conformations A and C were strongly favored in d(6)-DMSO because of hydrogen bonding interactions with the solvent. The syntheses of 6 and 7 reported herein are expected to facilitate the design and synthesis of analogs of the calicheamicin aryl tetrasaccharide 3, which should prove useful in further analysis and applications of oligosaccharides as DNA binders.

  DOI：

  10.1021/jo00109a008

文献信息

• Chemoselective allylation of aldehydes using cerium(III) chloride: simple synthesis of homoallylic alcohols
  作者：J.S. Yadav、B.V.S. Reddy、G. Kondaji、J. Shyam Sunder Reddy

  DOI：10.1016/j.tet.2004.11.029

  日期：2005.1

  Aldehydes undergo smooth nucleophilic addition with allyltributylstannane in the presence of CeCl3·7H2O in acetonitrile under extremely mild reaction conditions to afford the corresponding homoallylic alcohols in excellent yields with high chemoselectivity. This method is very useful especially for the allylation of aldehydes bearing acid sensitive functionalities such as TBDMS, THP ethers, acetonides

  在极为温和的反应条件下，在乙腈中CeCl 3 ·7H 2 O的存在下，醛与烯丙基三丁基锡烷进行平滑的亲核加成反应，从而以高收率和高化学选择性提供相应的均丙醇。该方法对于将带有酸敏感性官能团的醛（如TBDMS，THP醚，丙酮化物，芳基烷基醚和氨基甲酸酯）进行烯丙基化非常有用。
• Regiocontrolled Synthesis of the Antitumor Antibiotic AT2433-A1
  作者：John D. Chisholm、David L. Van Vranken

  DOI：10.1021/jo000911r

  日期：2000.11.1

  The indolo[2,3-a]carbazole glycosides are potent antitumor antibiotics currently undergoing clinical trials for the treatment of numerous types of cancer. AT2433-A1 is the most complex member of this family of compounds possessing a unique disaccharide with a sensitive aminodeoxysugar and an unsymmetric aglycon. The synthesis of this natural product requires a method for glycosylation that sets the

  吲哚[2，3-a]咔唑糖苷是有效的抗肿瘤抗生素，目前正接受临床试验以治疗多种类型的癌症。AT2433-A1是该化合物家族中最复杂的成员，具有独特的二糖以及敏感的氨基脱氧糖和不对称糖苷配基。这种天然产物的合成需要糖基化的方法，该方法设定异头异构中心的立体化学和糖苷配基的区域化学。这些目标是通过对bis-3，4-（3-吲哚基）琥珀酰亚胺进行曼尼希环化反应而得到的，主要的二氢吲哚中间体可以与复杂的碳水化合物被立体选择性地糖基化，而没有羟基的保护或活化。通过在动力学或热力学条件之间进行选择，可以精确地控制曼尼希环化反应的区域化学。该策略最终导致抗肿瘤抗生素AT2433-A1的首次合成。
• Conformationally constrained amino acids: enantiodivergent synthesis of all four stereoisomers of 2-(tetrahydrofuran-2-yl)glycine
  作者：Aigars Jirgensons、Maura Marinozzi、Roberto Pellicciari

  DOI：10.1016/j.tet.2004.10.091

  日期：2005.1

  The first enantiodivergent synthesis of all four possible 2-(tetrahydrofuran-2-yl)glycine stereoisomers is described. The key step of the route is the highly stereocontrolled allylboration of the (S)- or (R)-Garner's aldehydes to give four chiral homoallylalcohols. Starting from them, the title compounds are obtained in five steps.

  描述了所有四种可能的2-（四氢呋喃-2-基）甘氨酸立体异构体的第一对映异构体合成。该路线的关键步骤是高度立体控制的（S）-或（R）-加纳尔醛的烯丙基硼化反应，得到四种手性均烯丙基醇。从它们开始，可以通过五个步骤获得标题化合物。
• Oxidase Heterotetramer Completes 1-Azabicyclo[3.1.0]hexane Formation with the Association of a Nonribosomal Peptide Synthetase
  作者：Yiyuan Cheng、Xuan Yi、Yan Zhang、Qingli He、Dandan Chen、Weiguo Cao、Pengfei Fang、Wen Liu

  DOI：10.1021/jacs.2c12507

  日期：2023.4.26

  acid (DADH); however, the process through which linear DADH is cyclized to furnish an ABCH ring system remains poorly understood. Based on the reconstitution of the route of the ABCH-containing unit by blending genes/enzymes involved in the biosynthesis of ficellomycin and azinomycins, we report that ABCH formation is completed by an oxidase heterotetramer with the association of a nonribosomal peptide

  Ficellomycin、azinomycins 和 vazabitide A 是非核糖体肽天然产物，其特征在于氨基酸单元包含类似的 1- a za b i c yclo [3.1.0] h exane (ABCH) 药效团。该单元源自d i a mino- d ihydroxy- h庚酸 (DADH)；然而，线性 DADH 环化以提供 ABCH 环系统的过程仍然知之甚少。基于通过混合参与 ficellomycin 和 azinomycins 生物合成的基因/酶重建含 ABCH 单元的路线，我们报告 ABCH 形成是由氧化酶异四聚体与非核糖体肽合成酶 (NRPS) 结合完成的。DADH 前体在大肠杆菌中制备，以产生经过体外处理的缀合物用于从氨基载体蛋白上卸载的酶促水解。为了提供氮丙啶环，DADH 通过 C7-羟基磺化和硫酸盐消除偶联环化处理。进一步环化导致氮杂双环己烷药效团被证明发生在 NRPS
• Diastereoselection during 1,2-Addition of the Allylindium Reagent to α-Thia and α-Amino Aldehydes in Aqueous and Organic Solvents
  作者：Leo A. Paquette、Thomas M. Mitzel、Methvin B. Isaac、Curtis F. Crasto、William W. Schomer

  DOI：10.1021/jo970274d

  日期：1997.6.1

  The stereochemistry of the indium-promoted reaction of allyl bromide with alpha-thia (PhS and MeS), disubstituted alpha-amino (Bn2N, Me2N, isoindolyl), and protected alpha-amino aldehydes (Ac and Boc) in water has been evaluated. The reactions involving the sulfur derivatives are minimally diastereoselective, indicating that the allylindium reagent is not thiophilic. Chelation is not observed and pi-facial discrimination is achieved via Felkin-Ahn transition states under the steric control of the substituents. The Garner aldehyde is also anti-diastereoselective. Interestingly, N-acetylmannosamine is appreciably responsive to chelation control and is capable of generating 90% of the syn beta-amino alcohol when reacted in a 0.5 M NH4Cl solution. While the alpha-dibenzylamino substituent is too bulky to enter into complexation, the alpha-dimethylamino group is not and can lead to high levels (99%) of syn diastereomer. The size of other neighboring substituents does have an impact on pi-facial discrimination in these systems and can erode the stereoselectivity accordingly.