(2R,6R)-2-methyl-6-(phenylmethoxy)-2H-pyran-3(6H)-one

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡喃
• 英文名称: (2R,6R)-2-methyl-6-(phenylmethoxy)-2H-pyran-3(6H)-one
• 英文别名: (2R,6R)-6-(benzyloxy)-2-methyl-2H-pyran-3(6H)-one；(2R,6R)-6-methyl-2-phenylmethoxy-2H-pyran-5-one
• 化学式: C₁₃H₁₄O₃
• 分子量: 218.252
• InChiKey: YJXXCWLEOFOZTP-ZWNOBZJWSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.9
• 重原子数：
  16
• 可旋转键数：
  3
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.31
• 拓扑面积：
  35.5
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  (2R,6R)-2-methyl-6-(phenylmethoxy)-2H-pyran-3(6H)-one 在 sodium tetrahydroborate 、 cerium(III) chloride 作用下， 生成 (2R,6R)-3,6-dihydro-2-methyl-6-(phenylmethoxy)-2H-pyran-3-ol
  参考文献：
  名称：

  De Novo Synthesis of the Trisaccharide Subunit of Landomycins A and E

  摘要：

  A highly enantio- and diastereoselective synthesis of alpha-L-rhodinose, beta-D-olivose as well as the trisaccharide portion of landomycin A from achiral acetyl furan has been developed. The key transformations include the palladium-catalyzed glycosylation, Myers' reductive rearrangement, diastereoselective dihydroxylation, and regioselective Mitsunobu inversion. A Mitsunobu reaction on a six member ring cis-1,2-diol was found to chemoselectively discriminate between equatorial and axial alcohols and to stereoselectively convert cis-1,2-diol into ant 1,2-diol.

  DOI：

  10.1021/ol800697k
• 作为产物：
  描述：

  (2R)-2-tert-butyldimethylsilanyloxymethyl-6-hydroxy-6H-pyran-3-one 在 tris(dibenzylideneacetone)dipalladium(0) chloroform complex sodium acetate 、 三苯基膦 作用下， 以 二氯甲烷 、 苯 为溶剂， 反应 4.0h， 生成 (2R,6R)-2-methyl-6-(phenylmethoxy)-2H-pyran-3(6H)-one
  参考文献：
  名称：

  从头开始的2-Deoxy-β-糖苷方法：地高糖和Digitoxin 1的不对称合成

  摘要：

  已经开发出了高度对映选择性和直接的途径来制备三糖天然产物地高糖和洋地黄毒苷。该方法的关键是钯催化糖基化反应，还原性1,3-移位，非对映选择性二羟基化和区域选择性保护的迭代应用。天然产物digoxose的第一全合成是在非手性从2- acylfuran 19个总步骤完成，和洋地黄毒苷在15个步骤塑成从洋地黄毒苷开始2和吡喃酮8 β。这种灵活的合成策略还允许制备地高糖和洋地黄毒苷的单糖和二糖类似物。

  DOI：

  10.1021/jo062534+

文献信息

• Divergent de novo synthesis of all eight stereoisomers of 2,3,6-trideoxyhexopyranosides and their oligomers
  作者：Wangze Song、Yu Zhao、John C. Lynch、Hyunjin Kim、Weiping Tang

  DOI：10.1039/c5cc07787g

  日期：——

  All eight possible stereoisomers of 2,3,6-trideoxyhexopyranosides are prepared systematically from furan derivatives by a sequence of Achmatowicz rearrangement, Pd-catalysed glycosidation, and chiral catalyst-controlled tandem reductions. This sequence provides access to...

  通过呋喃衍生物的一系列Achmatowicz重排，Pd催化的糖苷化和手性催化剂控制的串联还原反应，系统地从呋喃衍生物中制备了2,8,3,6-三甲氧基己吡喃糖苷的所有八种可能的立体异构体。通过此序列可以访问...
• Chiral Catalyst-Directed Dynamic Kinetic Diastereoselective Acylation of Lactols for <i>De Novo</i> Synthesis of Carbohydrate
  作者：Hao-Yuan Wang、Ka Yang、Dan Yin、Can Liu、Daniel A. Glazier、Weiping Tang

  DOI：10.1021/acs.orglett.5b02641

  日期：2015.11.6

  major challenges of synthetic carbohydrate chemistry. We have developed a new strategy consisting of a chiral catalyst-directed acylation followed by a palladium-catalyzed glycosidation to achieve high α- and β-stereoselectivity on the anomeric position. The former process involves a dynamic kinetic diastereoselective acylation of lactols derived from Achmatowicz rearrangement, while the latter is a stereospecific

  将立体化学控制在异头位置仍然是合成碳水化合物化学的主要挑战之一。我们已经开发了一种新的策略，包括手性催化剂导向的酰化反应，然后钯催化的糖苷化，以在异头位置实现高α-和β-立体选择性。前者涉及衍生自Achmatowicz重排的乳醇的动态动力学非对映选择性酰化反应，而后者是立体有规钯催化的烯丙基烷基化反应。
• Catalytic Asymmetric Synthesis of All Possible Stereoisomers of 2,3,4,6-Tetradeoxy-4-Aminohexopyranosides
  作者：Zhongpeng Zhu、Daniel A. Glazier、Daoshan Yang、Weiping Tang

  DOI：10.1002/adsc.201800029

  日期：2018.6.5

  strategy for the synthesis of all eight possible 2,3,6‐trideoxyhexopyranosides with three stereogenic centers. However, the diastereoselectivity for one of the three stereogenic centers was low and it was not controlled by catalysts. In this update, we described a systematic method for the first catalytic asymmetric synthesis of all eight possible 2,3,6‐trideoxyhexopyranosides and all eight possible

  我们最近开发了一种不同的策略，用于合成具有三个立体异构中心的所有八种可能的2,3,6-三苯氧基己吡喃糖苷。但是，三个立体异构中心之一的非对映选择性很低，并且不受催化剂控制。在此更新中，我们描述了一种系统的方法，用于所有八种可能的2,3,6-三苯氧基己吡喃糖苷和所有八种可能的2,3,4,6-四脱氧-4-氨基己基吡喃糖苷的首次催化不对称合成。从该策略衍生的产品包括天然产品Grecocycline A，spinosyn A和ossamycin的糖苷。每个产品中的所有三个立体异构中心均由一对手性催化剂控制。成功的关键是应用我们最近开发的Achmatowicz重排产物的动态动力学立体发散酰化反应和手性催化剂导向的还原反应。2,3,4,6-四脱氧-4-氨基糖的简单二甲基化作用提供了天然存在的β-D-异丁香胺和β-L-os苷的衍生物。
• A Direct Comparison of the Anticancer Activities of Digitoxin MeON-Neoglycosides and <i>O</i>-Glycosides
  作者：Anand Krishnan V. Iyer、Maoquan Zhou、Neelam Azad、Hosam Elbaz、Leo Wang、Derek K. Rogalsky、Yon Rojanasakul、George A. O'Doherty、Joseph M. Langenhan

  DOI：10.1021/ml1000933

  日期：2010.10.14

  Digitoxin is a cardiac glycoside currently being investigated for potential use in oncology; however, an investigation of anticancer activity as a function, of oligosaccharide chain length has not yet been performed. We generated mono-, di-, and tri-O-digitoxoside derivatives, of digitoxin and compared their activities to the corresponding MeON-neoglycosides. Both classes of cardenolide derivatives display comparable oligosaccharide chain length-dependent cytotoxicity toward human cancer cell lines. Further investigation revealed that both classes of compounds induce caspase-9-mediated apoptosis in non-small cell lung cancer cells (NCI-H460). Because O-glycosides and MeON-neoglycosides share a similar mode of action, the convenience of MeON-neoglycosylation could be exploited in future SAR work to rapidly survey large numbers of carbohydrates to prioritize selected O-glycoside candidates for traditional synthesis.