tert-butyl (1R,2S)-2-hydroxy-1-(hydroxymethyl)-3-butenylcarbamate | 114301-36-9

• 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: tert-butyl (1R,2S)-2-hydroxy-1-(hydroxymethyl)-3-butenylcarbamate
• 英文别名: N-Boc-(2R,3S)-2-aminopent-4-en-1,3-diol；tert-butyl [(2R,3S)-1,3-dihydroxypent-4-en-2-yl]carbamate；tert-butyl N-[(2R,3S)-1,3-dihydroxypent-4-en-2-yl]carbamate
• CAS: 114301-36-9
• 化学式: C₁₀H₁₉NO₄
• 分子量: 217.265
• InChiKey: DZUUXUNYNBTANP-SFYZADRCSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.3
• 重原子数：
  15
• 可旋转键数：
  6
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.7
• 拓扑面积：
  78.8
• 氢给体数：
  3
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  tert-butyl (1R,2S)-2-hydroxy-1-(hydroxymethyl)-3-butenylcarbamate 在 咪唑 、 acetylacetonatodicarbonylrhodium(l) 、 BIPHRPHOS 、 氢气 作用下， 以 四氢呋喃 为溶剂， 65.0 ℃ 、202.65 kPa 条件下， 反应 16.0h， 生成 (2R,3S)-3-(tert-Butyl-dimethyl-silanyloxy)-2-(tert-butyl-dimethyl-silanyloxymethyl)-6-ethoxy-piperidine-1-carboxylic acid tert-butyl ester
  参考文献：
  名称：

  Rhodium-Catalyzed Cyclohydrocarbonylation:  Application to the Synthesis of (+)-Prosopinine and (−)-Deoxoprosophylline

  摘要：

  Efficient convergent total syntheses of (+)-prosopinine (1) and (-)-deoxoprosophylline (4) were accomplished using Rh-BIPHEPHOS complex-catalyzed cyclohydrocarbonylation as the key step. The Rh-BIPHEPHOS complex-catalyzed cyclohydrocarbonylation of I, derived from (R)-serine, at 65 degrees C and 4 atm of CO and H-2 (1:1) in ethanol afforded 6-ethoxypiperidine II, which was transformed to enantiopure (+)-prosopinine (1) in 3 steps. In a similar manner, (-)-deoxoprosophylline was synthesized through cyclohydrocarbonylation of IV derived from (S)-serine, giving 6-ethoxypiperidine V. The key intermediate V was transformed to enantiopure (-)-deoxoprosophylline (4) in 4 steps. These two short total syntheses clearly demonstrate the usefulness of the extremely regioselective cyclohydrocarbonylation process developed in these laboratories for the concise syntheses of piperidine alkaloids and related compounds.

  DOI：

  10.1021/jo9815608
• 作为产物：
  描述：

  以93的产率得到tert-butyl (1R,2S)-2-hydroxy-1-(hydroxymethyl)-3-butenylcarbamate
  参考文献：
  名称：

  Eur. J. Org. Chem. 2009, 4221-4224

  摘要：

  DOI：

文献信息

• Development of a Highly β-Selective Ribosylation Reaction without Using Neighboring Group Participation:  Total Synthesis of (+)-Caprazol, a Core Structure of Caprazamycins
  作者：Shinpei Hirano、Satoshi Ichikawa、Akira Matsuda

  DOI：10.1021/jo701699h

  日期：2007.12.1

  (+)-caprazol are described. The key elements of our approach include the early stage introduction of the aminoribose in a highly β-selective manner, using the steric hindrance in the transition state and the construction of the diazepanone by a modified intramolecular reductive amination. The 5‘-C-glycyluridine derivative 9, which was prepared stereoselectively via Sharpless asymmetric aminohydroxylation,

  描述了（+）-辣椒碱的全合成的全部细节。我们方法的关键要素包括：以过渡型空间位阻，以高度β-选择性的方式早期引入氨基核糖，以及通过修饰的分子内还原胺化作用构建二氮杂酮。经由Sharpless不对称氨基羟基化立体选择性地制备的5'- C-甘氨酰尿苷衍生物9被2,3- O-亚烷基核呋喃糖基供体核糖化。揭示了增加缩醛单元的烷基取代基的尺寸导致改善了端基异构体位置的立体选择性，以及所需的核糖苷21b（1′′-β）和22b。当使用具有更空间位阻的3-亚戊基的核糖基氟化物16时，以80％的收率获得（1′′-α）（21b / 22b＝ 24.0 / 1）。还讨论了核糖基化的立体选择性的起源。使用模型醛37优化了二氮杂酮系统的构建，并通过包括催化加氢然后进行氢化物还原的两步反应序列，以88％的收率获得了所需的二氮杂酮38。将该方法应用于醛44可成功获得二氮杂酮衍生物45和46。，其官能团操作完成了（+）-卡巴唑的全部合成。
• Synthesis of Polyhydroxylated Pyrrolizidine Alkaloids of the Alexine Family by Tandem Ring-Closing Metathesis−Transannular Cyclization. (+)-Australine
  作者：James D. White、Peter Hrnciar

  DOI：10.1021/jo0012748

  日期：2000.12.1

  9 via oxazolidinones 15 and 51, respectively, underwent ring-closing metathesis with Grubbs's catalyst to give azacyclooctenes 26 and 55. Treatment of each azacyclooctene with m-chloroperoxybenzoic acid afforded beta-epoxide 28 from 26 and alpha-epoxide 61 from 60. Basic hydrolysis of each of these oxazolidinones was accompanied by transannular attack at the epoxide by nitrogen, resulting in 2-(O-b

  由环氧醇9分别经由恶唑烷酮15和51制备的二烯23和54，用Grubbs的催化剂进行闭环易位，得到氮杂环辛烯26和55。用间氯过氧苯甲酸处理每种氮杂环辛烯得到26和26的β-环氧化物28。 60的α-环氧化物61。每一种恶唑烷酮的碱性水解都伴随着氮对环氧化物的环过环进攻，从而产生2-（O-苄基）-7-脱氧阿瑞辛（29）和1,2-二-（O -苄基）australine（62）。后者在氢解后转化为生物碱澳大林碱（3）。尝试实现二烯37、38和46的闭环易位的尝试失败，这表明，尽管Grubbs的催化剂可以耐受一个烯丙基氧取代基，但两个不能。
• Unified Synthesis of Densely Functionalized Amino Acid Building Blocks for the Preparation of Caprazamycin Nucleoside Antibiotics
  作者：Ruth Linder、Christian Ducho

  DOI：10.1002/ejoc.201801667

  日期：2019.2.21

  The total synthesis of caprazamycin nucleoside antibiotics and their analogues is not trivial. For instance, it requires a densely functionalized amino acid building block to construct the diazepanone core motif. We now report a unified synthesis of five different amino acid building blocks of this type, thus providing a highly useful ′toolbox′ for the synthesis of caprazamycins as well as other complex

  辣椒素核苷抗生素及其类似物的总合成并非无关紧要。例如，它需要密集功能化的氨基酸构件来构建二氮杂酮核心基序。现在，我们报告了这种类型的五个不同氨基酸构建基的统一合成，从而为合成辣椒素和其他复杂的肽类天然产物提供了非常有用的“工具箱”。
• Stereocontrolled Total Synthesis of (+)-1-Deoxynojirimycin
  作者：Gregory Danoun、Julien Ceccon、Andrew E. Greene、Jean-François Poisson

  DOI：10.1002/ejoc.200900595

  日期：2009.9

  A highly efficient non-chiral-pool synthesis of (+)-1-deoxynojirimycin has been realized (24 % overall yield, 11 steps, complete stereocontrol). A novel one-pot enol ether metathesis/hydroboration/oxidation sequence is used for the selective formation of the all-trans cyclic triol. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009)

  已实现 (+)-1-脱氧野尻霉素的高效非手性池合成（总产率为 24%，11 个步骤，完全立体控制）。一种新型的一锅烯醇醚复分解/硼氢化/氧化序列用于选择性形成全反式环状三醇。(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009)
• Synthesis of an (<i>R</i>)-Garner-type Aldehyde from <scp>l</scp>-Serine: Useful Building Block for a (+)-Furanomycin Derivative
  作者：Giuseppe Bartoli、Giustino Di Antonio、Roberto Fiocchi、Sandra Giuli、Enrico Marcantoni、Mauro Marcolini

  DOI：10.1055/s-0028-1087851

  日期：——

  a new short synthesis of a useful intermediate, a 1,2-diprotected 2-aminopent-4-ene-1,3-diol, starting from the inexpensive natural amino acid l-serine, and via a Garner-type aldehyde. The (R)-α-amino aldehyde was obtained by the construction of an oxazoline ring between the N-protected amino group and the hydroxy group that resulted from reduction of the carboxylic acid functionality of l-serine.

  （+）-富拉霉素是一种在细菌蛋白翻译中替代1-异亮氨酸的抗生素。我们从廉价的天然氨基酸1-丝氨酸开始，并通过加纳型醛，在这里提出一种有用的中间体1,2-二保护的2-氨基戊-4-烯-1,3-二醇的新的短合成法。通过在N-保护的氨基和羟基之间构筑恶唑啉环而获得（R）-α-氨基醛，所述恶唑啉环是由1-丝氨酸的羧酸官能度降低引起的。 氨基酸-非对映选择性-镧系元素-天然产物-保护基-维蒂希反应