trans-6(S)-carbomethoxy-2-methoxy-5,6-dihydro-2H-pyran | 155976-23-1

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡喃
• 英文名称: trans-6(S)-carbomethoxy-2-methoxy-5,6-dihydro-2H-pyran
• 英文别名: (6S)-methoxy-3,6-dihydro-2H-pyran-(2S)-carboxylic acid methyl ester；methyl (2S,6S)-6-methoxy-3,6-dihydro-2H-pyran-2-carboxylate
• CAS: 155976-23-1
• 化学式: C₈H₁₂O₄
• 分子量: 172.181
• InChiKey: BEPDBZBIHYPLTB-BQBZGAKWSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.7
• 重原子数：
  12
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.62
• 拓扑面积：
  44.8
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  trans-6(S)-carbomethoxy-2-methoxy-5,6-dihydro-2H-pyran 在 lithium aluminium tetrahydride 作用下， 生成 (2S,6S)-6-hydroxymethyl-2-methoxy-5,6-dihydro-2H-pyran
  参考文献：
  名称：

  Asymmetric catalysis of Diels–Alder cycloaddition by a β-amino alcohol derived boron complex: reasonable transition-state assembly for one-directional diene approach

  摘要：

  由手性氨基醇衍生的硼络合物催化甘油酸与酸敏感的Danishefsky二烯的非对称Diels-Alder反应，实现了高对映选择性和cis(endo)非对映选择性，这是通过从邻近磺酰氨基的位点进行单向二烯接近的有利过渡态组装实现的。

  DOI：

  10.1039/c39940001563
• 作为产物：
  描述：

  甲基1,2,3,4-四-O-异丁酰基-beta-D-葡萄糖醛酸酯 在 palladium on activated charcoal 、 锌 3 Angstroem MS 、 三氟化硼乙醚 、 氢气 、 Vitamin B ₁₂ 、 氯化铵 、 1,8-二氮杂双环[5.4.0]十一碳-7-烯 、 溴化氢 作用下， 以 四氢呋喃 、 甲醇 、 二氯甲烷 、 异丙醇 为溶剂， 反应 0.08h， 生成 trans-6(S)-carbomethoxy-2-methoxy-5,6-dihydro-2H-pyran
  参考文献：
  名称：

  葡萄糖醛酸内酯方便地合成脱氧吡喃糖

  摘要：

  一个葡糖醛酸衍生物的特征的反应是4-（取代的）羟基的碱催化的消除，以生成Δ 4,5吡喃糖。氢化后，主要从α面开始，只要端基异构体构型为β，即可恢复初始C（5）构型。该序列提供了进入多个4-脱氧吡喃糖的途径：因此，通过在C（6）还原可容易地获得4-脱氧葡萄糖。转换为糖基，然后在C（2）/ C（3）处进行顺二羟基化反应，形成d- lyxo构型（在新霉素中发现）。最后，再次通过二羟基化显示出与KDO系列的不太明显的关系。

  DOI：

  10.1016/j.tetlet.2007.01.127

文献信息

• Enantioselective Hetero-Diels-Alder reaction with glyoxylate catalyzed by chiral titanium complex: asymmetric synthesis of the lactone portion of mevinolin and compactin
  作者：Masahiro Terada、Koichi Mikami、Takeshi Nakai

  DOI：10.1016/s0040-4039(00)92124-5

  日期：1991.2

  Asymmetric Diels-Alder reaction with methyl glyoxylate catalyzed by the chiral titanium complex 1 provides the dihydropyran carboxylate in high enantiomeric purity, which can be converted to the lactone portion of mevinolin or compactin.

  通过手性钛络合物1催化的乙醛酸甲酯与不对称Diels-Alder反应提供了高对映体纯度的二氢吡喃羧酸盐，其可以转化为美维林或紧密蛋白的内酯部分。
• Asymmetric Catalysis of Diels-Alder Cycloadditions by an MS-Free Binaphthol-Titanium Complex: Dramatic Effect of MS, Linear vs Positive Nonlinear Relationship, and Synthetic Applications
  作者：Koichi Mikami、Yukihiro Motoyama、Masahiro Terada

  DOI：10.1021/ja00086a014

  日期：1994.4

  Asymmetric Diels-Alder (D.-A.) reaction of 5-hydroxynaphthoquinone (juglone) with butadienyl acetate catalyzed by the binaphthol-derived chiral titanium (BINOL-Ti) complex 1 proceeds in only 9% ee in the presence of molecular sieves (MS). Remarkably, however, this reaction proceeds in 76-96% ee with BINOL-Ti complex 1 freed from MS to provide the endo-adducts useful for the synthesis of anthracyclines and tetracyclines. The solid MS-free BINOL-Ti complex 1 is stable for months at -20 degrees C, Enhancements in endo selectivity and asymmetric induction are observed with the MS-free BINOL-Ti 1 also in the catalyzed D.-A. cycloaddition of methacrolein and glyoxylate with 1,3-dienol ethers and esters. The glyoxylate adducts can be converted to the mevinolin (compactin) intermediates. Surprisingly, the MS-free complex 1 exhibits not only a linear relationship between the ee's of BINOL-Ti 1 and the D.-A. products but also a positive nonlinear effect (asymmetric amplification), depending simply on the mixing manner of (R)-1 with (S)-1 or (+/-)-1.
• Asymmetric catalysis of Diels–Alder cycloaddition by a β-amino alcohol derived boron complex: reasonable transition-state assembly for one-directional diene approach
  作者：Yukihiro Motoyama、Koichi Mikami

  DOI：10.1039/c39940001563

  日期：——

  Asymmetric Diels–Alder reactions of glyoxylate with acid-labile Danishefsky dienes are catalysed in high enantio- and cis(endo)-diastereo-selectivity by a chiral amino alcohol derived boron complex, via the favourable transition-state assembly for one-directional diene-approach from the site proximal to the sulfonylamino moiety.

  由手性氨基醇衍生的硼络合物催化甘油酸与酸敏感的Danishefsky二烯的非对称Diels-Alder反应，实现了高对映选择性和cis(endo)非对映选择性，这是通过从邻近磺酰氨基的位点进行单向二烯接近的有利过渡态组装实现的。
• Convenient syntheses of deoxypyranose sugars from glucuronolactone
  作者：Deborah Stanford (nee Sinnott)、Andrew V. Stachulski

  DOI：10.1016/j.tetlet.2007.01.127

  日期：2007.3

  acid derivatives is the base-catalysed elimination of a 4-(substituted) hydroxy group to generate a Δ4,5 pyranose. Following hydrogenation, proceeding mainly from the α-face provided the anomeric configuration is β, the initial C(5)-configuration is restored. This sequence affords access to a number of 4-deoxypyranoses: thus 4-deoxyglucoses are readily available by reduction at C(6). Conversion to a

  一个葡糖醛酸衍生物的特征的反应是4-（取代的）羟基的碱催化的消除，以生成Δ 4,5吡喃糖。氢化后，主要从α面开始，只要端基异构体构型为β，即可恢复初始C（5）构型。该序列提供了进入多个4-脱氧吡喃糖的途径：因此，通过在C（6）还原可容易地获得4-脱氧葡萄糖。转换为糖基，然后在C（2）/ C（3）处进行顺二羟基化反应，形成d- lyxo构型（在新霉素中发现）。最后，再次通过二羟基化显示出与KDO系列的不太明显的关系。