| 1133153-30-6

• 分子结构分类: 有机化合物 - 有机氧化合物
• CAS: 1133153-30-6
• 化学式: C₁₉H₄₂O₅Si₂
• 分子量: 406.71
• InChiKey: GULNZTJLCIEKOQ-JJTUDDRGSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.52
• 重原子数：
  26.0
• 可旋转键数：
  5.0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  57.15
• 氢给体数：
  1.0
• 氢受体数：
  5.0

反应信息

• 作为反应物：
  描述：

  在 lithium hexamethyldisilazane 作用下， 以 四氢呋喃 为溶剂， 反应 1.0h， 以85%的产率得到(2S,3R,4R,5R,6R)-4,5-bis[[tert-butyl(dimethyl)silyl]oxy]-2-methoxy-6-methyloxan-3-ol
  参考文献：
  名称：

  Stereoselective α-alkylation of methyl 6-deoxy-3,4-di-O-(tert-butyldimethylsilyl)-2-O-(2-methyl-3-oxobutanoyl)-α-d-glucopyranoside

  摘要：

  Allylation and benzylation at the alpha-carbon of alpha-methylated acetoacetyl (2-methyl-3-oxobutanoyl) group incorporated into the 2-OH of methyl 6-deoxy-3,4-O-(tert-butyldimethylsilyl)-alpha-D-glucopyranoside provided the respective alpha,alpha-differentially alkylated acetoacetyl derivatives, both with high diastereoselectivity. Thus-obtained doubly alkylated products possess an all-carbon quaternary stereogenic center with an absolute stereochemistry opposite to that introduced by using the 4-O-acetoacetyl regioisomer as the alkylation substrate. (C) 2008 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetlet.2008.12.091
• 作为产物：
  描述：

  methyl 6-deoxy-2,3-di-O-(tert-butyldimethylsilyl)-α-D-glucopyranoside 在 sodium methylate 作用下， 以 甲醇 为溶剂， 反应 15.0h， 以70%的产率得到
  参考文献：
  名称：

  Stereoselective α-alkylation of methyl 6-deoxy-3,4-di-O-(tert-butyldimethylsilyl)-2-O-(2-methyl-3-oxobutanoyl)-α-d-glucopyranoside

  摘要：

  Allylation and benzylation at the alpha-carbon of alpha-methylated acetoacetyl (2-methyl-3-oxobutanoyl) group incorporated into the 2-OH of methyl 6-deoxy-3,4-O-(tert-butyldimethylsilyl)-alpha-D-glucopyranoside provided the respective alpha,alpha-differentially alkylated acetoacetyl derivatives, both with high diastereoselectivity. Thus-obtained doubly alkylated products possess an all-carbon quaternary stereogenic center with an absolute stereochemistry opposite to that introduced by using the 4-O-acetoacetyl regioisomer as the alkylation substrate. (C) 2008 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetlet.2008.12.091

文献信息

• Stereoselective synthesis of highly enantioenriched 3-methyl-2-cyclohexen-1-ones possessing an asymmetric quaternary carbon as C-4 or C-6: a sugar template approach
  作者：Hiroto Kubo、Ikuko Kozawa、Ken-ichi Takao、Kin-ichi Tadano

  DOI：10.1016/j.tetlet.2007.12.031

  日期：2008.2

  a 3-methyl-2-cyclohexen-1-one-4- (or -6-) carboxylic acid as the O-4 ester, in which C-4 or C-6 is an asymmetric quaternary carbon. Removal of the sugar template from those aldol condensation products provided synthetically useful 3,6-dimethyl-2-cyclohexen-1-one-6-carboxylic acid and 3,4-dimethyl-2-cyclohexen-1-one-4-carboxylic acid derivatives both in high enantioenriched forms.

  由6-脱氧-2,3-二-O-（叔丁基二甲基甲硅烷基）-α-d-吡喃葡萄糖苷的C-4处的C-4掺入的α-甲基化乙酰乙酸酯生成的烯醇盐的1,4-加成，然后在两个碱介导的条件下将所得的1，4-加成产物进行羟醛缩合，提供具有高非对映选择性的4-O-官能化d-葡萄糖衍生物。这些产品将3-甲基-2-环己烯-1-酮-4-（或-6-）羧酸安装为O-4酯，其中C-4或C-6是不对称季碳原子。从那些醛醇缩合产物中除去糖模板提供了合成上有用的3,6-二甲基-2-环己烯-1-一-6-羧酸和3,4-二甲基-2-环己烯-1-一-4-羧酸都以高对映体富集的形式存在。