(S)-3-(tert-Butyl-dimethyl-silanyloxy)-2-hydroxy-pyrrolidine-1-carboxylic acid tert-butyl ester | 847942-52-3

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡咯烷类
• 英文名称: (S)-3-(tert-Butyl-dimethyl-silanyloxy)-2-hydroxy-pyrrolidine-1-carboxylic acid tert-butyl ester
• 英文别名: tert-butyl (3S)-3-[tert-butyl(dimethyl)silyl]oxy-2-hydroxypyrrolidine-1-carboxylate
• CAS: 847942-52-3
• 化学式: C₁₅H₃₁NO₄Si
• 分子量: 317.501
• InChiKey: GGTYLEYPMNZPEF-PXYINDEMSA-N

物化性质

• 沸点：
  358.5±42.0 °C(Predicted)
• 密度：
  1.03±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.34
• 重原子数：
  21
• 可旋转键数：
  5
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.93
• 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：

  (S)-3-(tert-Butyl-dimethyl-silanyloxy)-2-hydroxy-pyrrolidine-1-carboxylic acid tert-butyl ester 在 samarium diiodide 、 4-甲基苯磺酸吡啶 、 对甲苯磺酸 作用下， 以 四氢呋喃 、 二氯甲烷 为溶剂， 反应 24.17h， 生成 tert-butyl (2R,3S)-3-{[tert-butyl(dimethyl)silyl]oxy}-2-(hydroxymethyl)pyrrolidine-1-carboxylate
  参考文献：
  名称：

  Samarium Diiodide Promoted Generation and Asymmetric Hydroxyalkylation of N,O-Diprotected (3S)-3-Pyrrolidinol 2-Carbanions

  摘要：

  The N,O-diprotected chiral nonracemic 2-pyridyl 3-pyrrolidinol-2-yl sulfide 5a undergoes efficient SMl(2) mediated reduction to give the N,O-diprotected 3-pyrrolidinol 2-carbanion intermediate D, which reacted under Barbier-type conditions with ketones and alclehydes to afford the protected N-alpha-hydroxyalkyl-3-pyrrolidines 10b-h with excellent diastereoselectivity at the newly formed chiral center in the pyrrolidine ring. Application of the present method led to the formal asymmetric syntheses of (2R,3S)-2-hydroxymethyl-3-pyrrolidinol (2) and (2S,3S)-3hydroxyproline (12).

  DOI：

  10.1021/ol047733z
• 作为产物：
  描述：

  叔丁基二甲基氯硅烷 在 咪唑 、 4-二甲氨基吡啶 、 三乙基硼氢化锂 、 三乙胺 作用下， 以 四氢呋喃 、 二氯甲烷 、 N,N-二甲基甲酰胺 为溶剂， 反应 13.0h， 生成 (S)-3-(tert-Butyl-dimethyl-silanyloxy)-2-hydroxy-pyrrolidine-1-carboxylic acid tert-butyl ester
  参考文献：
  名称：

  使用三氟甲磺酸钪催化 N、O-缩醛和烯烃环化序列合成恶嗪支架的新方法

  摘要：

  一种通过三氟甲磺酸钪作为催化剂在二氯乙烷中在 60 °C下从 1,1-二取代烯烃和 N,O-缩醛制备[1,3]恶嗪-1-酮的新方法。该产品的结构很容易理解。该协议具有多种优点，例如非常温和的条件、廉价的起始材料和高产率。共调查22例，所有产品均经光谱方法确认。对三种化合物进行了单晶衍射。还在几个案例中研究了非对映化学。

  DOI：

  10.1016/j.tetlet.2023.154614

文献信息

• Sc(OTf)3-catalyzed intramolecular diastereoselective cyclization from tert-butoxycarbonyl to acyliminium ion
  作者：Zhuo-Ya Mao、Chen Wang、Xiao-Di Nie、Xiao-Li Han、Han-Qing Dong、Chang-Mei Si、Bang-Guo Wei

  DOI：10.1016/j.tet.2021.131959

  日期：2021.3

  An effective approach to access dyadic 1,3-oxazinan-2-ones 8a-8c and 4,4a,5,6-tetrahydro-[1,3]oxazino[3,4-a]quinolin-1(3H)-ones 8d-8h was developed through Sc(OTf)3-catalyzed intramolecular cyclization from tert-butoxycarbonyl to acyliminium ion 7a-7j. A variety of substituted N,O-acetals, with different ring size, proved to be suitable substrates for this transformation, and a series of (4aS,6S,7

  一种访问二元1,3-恶嗪南-2-酮8a - 8c和4,4a，5,6-四氢-[1,3]恶嗪基[3,4-a]喹啉-1（3H）-酮的有效方法8d-8h是通过Sc（OTf）3催化的分子内环化反应从叔丁氧羰基到酰基亚胺离子7a-7j的反应而开发的。各种具有不同环尺寸的取代的N，O-缩醛被证明是该转化的合适底物，并且一系列（4 aS， 6 S， 7 R）-6-OTBS-7-取代的六氢吡咯[1 ，2-c] [1,3] oxazin-1-ones 11a-11j和其他手性二元1,3-oxazinan-2-ones 8i，8j，11k以中等收率合成，具有非对映选择性（dr  > 99：1）。此外，通过这种有趣的路易斯酸催化的分子内环化过程获得了2，5-反式产物11a-11j。
• Stereoselective Synthesis of Pyrido- and Pyrrolo[1,2-<i>c</i>][1,3]oxazin-1-ones via a Nucleophilic Addition–Cyclization Process of <i>N</i>,<i>O</i>-Acetal with Ynamides
  作者：Pan Han、Zhuo-Ya Mao、Chang-Mei Si、Zhu Zhou、Bang-Guo Wei、Guo-Qiang Lin

  DOI：10.1021/acs.joc.8b02795

  日期：2019.1.18

  An efficient asymmetric approach to access functionalized pyrido- and pyrrolo[1,2-c][1,3]oxazin-1-ones has been developed through a nucleophilic addition–cyclization process of N,O-acetal with ynamides. A number of substituted ynamides 8a–8o and 3-silyloxypyrrolidine or piperidine N,O-acetals 6a, 7 were amenable to this transformation, and the desired products 9a–9o, 10a–10m were obtained with excellent

  通过N，O-乙缩醛与ynamides的亲核加成环化过程，已经开发出一种有效的不对称途径来获得官能化的吡啶并吡咯并[1,2- c ] [1,3]恶嗪-1-酮。许多取代的酰胺8a - 8o和3-甲硅烷氧基吡咯烷或哌啶N，O-缩醛6a和7都适合这种转化，并获得了所需的产物9a - 9o，10a - 10m，具有优异的区域选择性和出色的非对映选择性。此外，手性乙酰胺14a– 14f也可能会经历这种加成环化过程，从而以极高的收率获得15a – 15f产品。
• SmI₂-mediated intermolecular addition–elimination of piperidine and pyrrolidine <i>N</i>-α-radicals with arylacetylene sulfones
  作者：Chang-Hong Liu、Jia-Ming Guo、Xin Li、Jian-Ting Sun、Bang-Guo Wei、Chang-Mei Si

  DOI：10.1039/d2cc03984b

  日期：——

  An efficient approach to access α-arylacetylene-substituted pyrrolidine and piperidine derivatives has been developed through a samarium diiodide-mediated addition–elimination process of pyrrolidine and piperidine N-α-radicals with arylacetylene sulfones.

  通过二碘化钐介导的吡咯烷和哌啶N -α-自由基与芳基乙炔砜的加成-消除过程，开发了一种获得 α-芳基乙炔取代的吡咯烷和哌啶衍生物的有效方法。
• SmI₂-Mediated Radical Cross-Couplings of α-Hydroxylated Aza-hemiacetals and<i>N</i>,<i>S</i>-Acetals with α,β-Unsaturated Compounds: Asymmetric Synthesis of (+)-Hyacinthacine A₂, (−)-Uniflorine A, and (+)-7-<i>epi</i>-Casuarine
  作者：Xue-Kui Liu、Shi Qiu、Yong-Gang Xiang、Yuan-Ping Ruan、Xiao Zheng、Pei-Qiang Huang

  DOI：10.1021/jo200600n

  日期：2011.6.17

  The SmI2-mediated radical coupling reactions of beta-hydroxylated pyrrolidine/piperidine aza-hemiacetals 8 and 9 and N,S-acetals 6 and 33 with alpha/beta-unsaturated compounds are described. This method allows a rapid access to beta-hydroxylated pyrrolidines, piperidines, pyrrolizidinones, and indolizidinones. Starting from N,S-acetal 33 and via a common intermediate 27, the alkaloids hyacinthacine A(2) (2), uniflorine A (3, 6-epi-casuarine), and the unnatural epimer 7-epi-casuarine (37) have been synthesized in four and five steps with overall yields of 34%, 16%, and 13%, respectively. The radical mechanism of the coupling reactions has been confirmed by controlled experiments, which also allowed deducing the anionic mechanism in the coupling between N,S-acetal 6 and carbonyl compounds. This demonstrates that the mechanisms of these SmI2-mediated reactions are switchable from Barbier-type anionic to radical by cooperative action of BF3 center dot OEt2 and t-BuOH.