2-({[tert-butyl(dimethyl)silyl]oxy}methyl)-5-hydroxy-4H-pyran-4-one | 250351-17-8

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡喃
• 英文名称: 2-({[tert-butyl(dimethyl)silyl]oxy}methyl)-5-hydroxy-4H-pyran-4-one
• 英文别名: 2-[[Tert-butyl(dimethyl)silyl]oxymethyl]-5-hydroxypyran-4-one
• CAS: 250351-17-8
• 化学式: C₁₂H₂₀O₄Si
• 分子量: 256.374
• InChiKey: ITWWQOLWJZRPHH-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.87
• 重原子数：
  17
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.58
• 拓扑面积：
  55.8
• 氢给体数：
  1
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  2-({[tert-butyl(dimethyl)silyl]oxy}methyl)-5-hydroxy-4H-pyran-4-one 在 四丁基氟化铵 、 sodium hydride 、 caesium carbonate 、 三乙胺 作用下， 以 四氢呋喃 、 DMF (N,N-dimethyl-formamide) 、 二氯甲烷 为溶剂， 反应 24.67h， 生成 methanesulfonic acid 4-oxo-5-[5-(7-trifluoromethyl-quinolin-4-ylsulfanyl)-pentyloxy]-4H-pyran-2-ylmethyl ester
  参考文献：
  名称：

  [EN] COMPOUNDS AND METHODS OF TREATING CELL PROLIFERATIVE DISEASES, RETINOPATHIES AND ARTHRITIS
  [FR] NOUVEAUX COMPOSES ET PROCEDES DE TRAITEMENT DE PATHOLOGIES ASSOCIEES A LA PROLIFERATION CELLULAIRE, DE RETINOPATHIES ET DE L'ARTHRITE

  摘要：

  公开号：

  WO2004076445A3
• 作为产物：
  描述：

  5-(tert-butyldimethylsilyloxy)-2-(tert-butyldimethylsilyloxy)methyl-4H-pyran-4-one 在 caesium carbonate 作用下， 以 水 、 N,N-二甲基甲酰胺 为溶剂， 以95%的产率得到2-({[tert-butyl(dimethyl)silyl]oxy}methyl)-5-hydroxy-4H-pyran-4-one
  参考文献：
  名称：

  A convenient synthesis of 5-arylamino-4H-pyran-4-ones using palladium-catalyzed amination

  摘要：

  A concise approach to 5-arylamino-4H-pyran-4-ones is described via palladium-catalyzed amination reaction. The methodology involved in this Letter is based on protection/deprotection protocols and on manipulation of the 5-hydroxy group of readily available kojic acid. It would provide a new entry to a range of 5-arylamino-4H-pyran-4-ones via Buchwald-Hartwig-type amination reaction on 4H-pyran-4-one unit. (C) 2009 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetlet.2009.07.139

文献信息

• Selective protection of either the phenol or the hydroxy group in hydroxyalkyl phenols
  作者：Michael Sefkow、Helvi Kaatz

  DOI：10.1016/s0040-4039(99)01391-x

  日期：1999.9

  Hydroxyalkyl phenols can be protected either at the hydroxy group or at the phenol in a simple protocol (CH2Cl2, Et3N, DMAP, 0 °C → room temp.) by using either t-butyldimethylsilyl chloride or trityl chloride as protecting reagent. Yields are in the range of 37–92%.

  通过使用叔丁基二甲基氯硅烷或三苯甲基氯作为保护剂，可以通过简单的操作规程（CH 2 Cl 2，Et 3 N，DMAP，0°C→室温）在羟基或苯酚上保护羟基烷基苯酚。试剂。产率在37-92％的范围内。
• An Enantioselective Claisen Rearrangement Catalyzed by N-Heterocyclic Carbenes
  作者：Juthanat Kaeobamrung、Jessada Mahatthananchai、Pinguan Zheng、Jeffrey W. Bode

  DOI：10.1021/ja103631u

  日期：2010.7.7

  of a chiral azolium salt (10 mol %), enols and ynals undergo a highly enantioselective annulation reaction to form enantiomerically enriched dihydropyranones via an N-heterocyclic carbene catalyzed variant of the Claisen rearrangement. Unlike other azolium-catalyzed reactions, this process requires no added base to generate the putative NHC-catalyst, and our investigations demonstrate that the counterion

  在手性唑盐 (10 mol%) 的存在下，烯醇和炔醇发生高度对映选择性的环化反应，通过 N-杂环卡宾催化的克莱森重排变体形成富含对映体的二氢吡喃酮。与其他唑鎓催化反应不同，该过程不需要添加碱来生成假定的 NHC 催化剂，我们的研究表明，唑鎓盐的抗衡离子在催化活性物质的形成中起着关键作用。详细的动力学研究消除了潜在的 1,4-加成机制；观察到的速率定律和激活参数与作为限速步骤的克莱森重排一致。该催化体系用于合成富含对映体的曲酸衍生物，
• Enantioselective 1,4-addition of kojic acid derivatives to β-nitroolefins catalyzed by a cinchonine derived sugar thiourea
  作者：B. V. Subba Reddy、S. Madhusudana Reddy、Manisha Swain、Srikanth Dudem、Shasi V. Kalivendi、C. Suresh Reddy

  DOI：10.1039/c3ra47423b

  日期：——

  A highly enantioselective Michael addition reaction of kojic acid derivatives to β-nitroolefins has been accomplished using a cinchonine derived sugar thiourea. The reaction provides the corresponding Michael adducts in excellent yields with a high degree of enantioselectivity (up to 99% ee) in short reaction time with low catalyst loading. The Michael adducts are found to exhibit promising cytotoxicity

  使用辛可宁衍生的糖硫脲已经完成了曲酸衍生物对β-硝基烯烃的高度对映选择性迈克尔加成反应。该反应在短的反应时间内以低的催化剂载量以优异的产率提供了高产率的对映体选择性（高达99％ee）的相应的迈克尔加合物。发现迈克尔加合物对各种癌细胞系显示出有希望的细胞毒性。
• Asymmetric Michael/hemiketalization of 5-hydroxy-2-methyl-4H-pyran-4-one to β,γ-unsaturated α-ketoesters catalyzed by a bifunctional rosin–indane amine thiourea catalyst
  作者：B. V. Subba Reddy、Manisha Swain、S. Madhusudana Reddy、J. S. Yadav、B. Sridhar

  DOI：10.1039/c4ra06938b

  日期：——

  A highly efficient enantioselective Michael-hemiketalization cascade process is reported using a chiral bifunctional rosin–indane amine thiourea catalyst.

  报道了一种使用手性双功能松香-茚胺硫脲催化剂的高效对映选择性Michael-半缩醛化级联过程。
• Organocatalytic enantioselective Michael addition of a kojic acid derivative to nitro olefins
  作者：Jiyu Wang、Qing Zhang、Hui Zhang、Yujun Feng、Weicheng Yuan、Xiaomei Zhang

  DOI：10.1039/c2ob07192d

  日期：——

  By employing a chiral bifunctional thiourea–tertiary amine as catalyst, enantioselective Michael addition of a kojic acid derivative to nitro olefins was realised. The reactions afforded the products with good yields (up to 99%) in good enantioselectivities (up to 97% ee). In addition, the absolute configuration of one product was determined.

  通过采用手性双官能团 硫脲以叔胺为催化剂，实现了将曲酸衍生物对硝基烯烃的对映选择性迈克尔加成反应。反应提供了具有良好对映选择性（高达97％ee）的良好产率（高达99％）的产物。另外，确定一种产品的绝对构型。