(4S,5R)-2,2-dimethyl-5-((4R,5S)-2,2,5-trimethyl-1,3-dioxolan-4-yl)-1,3-dioxolane-4-carbaldehyde | 212065-83-3

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (4S,5R)-2,2-dimethyl-5-((4R,5S)-2,2,5-trimethyl-1,3-dioxolan-4-yl)-1,3-dioxolane-4-carbaldehyde
• 英文别名: (2S,3R)-2,2-dimethyl-5-((4'R,5'S)-2',2',5'-trimethyl-1',3'-dioxolan-4'-yl)-1,3-dioxolane-4-carbaldehyde；Di-O-isopropylidene-L-fucose；2,3:4,5-di-O-isopropylidene-L-fucose；(4S,5R)-2,2-dimethyl-5-[(4R,5S)-2,2,5-trimethyl-1,3-dioxolan-4-yl]-1,3-dioxolane-4-carbaldehyde
• CAS: 212065-83-3
• 化学式: C₁₂H₂₀O₅
• 分子量: 244.288
• InChiKey: VPVMWKGSICGKCH-JLIMGVALSA-N

物化性质

• 熔点：
  62-64 °C
• 沸点：
  299.3±40.0 °C(Predicted)
• 密度：
  1.117±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  0.7
• 重原子数：
  17
• 可旋转键数：
  2
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.92
• 拓扑面积：
  54
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  (4S,5R)-2,2-dimethyl-5-((4R,5S)-2,2,5-trimethyl-1,3-dioxolan-4-yl)-1,3-dioxolane-4-carbaldehyde 在 Dowex (50W X₈, H⁺ form) 作用下， 以 水 为溶剂， 反应 24.0h， 以74%的产率得到L(-)岩藻糖
  参考文献：
  名称：

  l-Fucose from Vitamin C with Only Acetonide Protection

  摘要：

  Addition of human milk oligosaccharides (HMO) to baby foods may protect infants from disease. As many simple HMOs are fucosylated this is likely to increase the demand for L-fucose as a synthetic building block. Any chemical synthesis must be cheap to compete with a biotechnological process. Acetonide is the only protecting group we have used in this new synthesis of L-fucose from vitamin C in 27% overall yield (purification by recrystallization; no chromatography required in the entire sequence).

  DOI：

  10.1021/ol502733x
• 作为产物：
  描述：

  山梨酸乙酯 在 四氧化锇 、 (DHQ)2-PHAL 、 甲基磺酰胺 、 potassium carbonate 四氧化锇 、 草酰氯 、 甲基磺酰胺 、 camphor-10-sulfonic acid 、 二异丁基氢化铝 、 potassium carbonate 、 对甲苯磺酸 、 二甲基亚砜 、 氢化奎尼定 1,4-(2,3-二氮杂萘)二醚 、 三乙胺 、 potassium hexacyanoferrate(III) 作用下， 以 四氢呋喃 、 二氯甲烷 、 水 、 甲苯 、 叔丁醇 为溶剂， 反应 39.5h， 生成 (4S,5R)-2,2-dimethyl-5-((4R,5S)-2,2,5-trimethyl-1,3-dioxolan-4-yl)-1,3-dioxolane-4-carbaldehyde
  参考文献：
  名称：

  Enantioselective Synthesis of 10-epi-Anamarine via an Iterative Dihydroxylation Sequence

  摘要：

  The enantioselective syntheses of 10-epi-anamarine and 5,10-epi,epi-anamarine have been achieved in 13 to 14 steps. The route relies upon an enantio- and regioselective Sharpless dihydroxylation of either dienoates or trienoates to establish the C-8 to C-11 stereochemistry. A diastereoselective Leighton allylation established the desired C-5 stereochemistry. The route also relies upon a ring-closing metathesis to establish the alpha,beta-unsaturated lactones.

  DOI：

  10.1021/ol047322i

文献信息

• METHOD FOR PRODUCING L-FUCOSE
  申请人：Schroven Andreas

  公开号：US20130245250A1

  公开（公告）日：2013-09-19

  Method for producing L-fucose includes in a first aspect, a method for the preparation of L-fucose, wherein L-fucose precursors are produced from pectin and L-fucose is produced from the L-fucose precursors; in a second aspect, a method for the preparation of L-fucose from D-galacturonic acid or a salt thereof, wherein L-fucose precursors are produced from D-galacturonic acid of a salt thereof, and L-fucose is produced from the L-fucose precursors; and an L-fucose precursor as shown in Formula A, wherein R is a linear or branched chain saturated hydrocarbon group with 1-6 carbon atoms, such as methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, s-butyl, t-butyl, n-hexyl, etc., preferably a methyl group.

  生产L-岩藻糖的方法包括第一方面，一种制备L-岩藻糖的方法，其中L-岩藻糖前体从果胶中产生，并且L-岩藻糖从L-岩藻糖前体中产生；第二方面，一种从D-半乳糖酸或其盐制备L-岩藻糖的方法，其中L-岩藻糖前体从D-半乳糖酸或其盐中产生，并且L-岩藻糖从L-岩藻糖前体中产生；以及如公式A所示的L-岩藻糖前体，其中R是线性或支链饱和碳原子数为1-6的烷基羟基烃基，例如甲基、乙基、正丙基、异丙基、正丁基、异丁基、正丁基、叔丁基、正己基等，最好是甲基。
• Acetonation of l-pentoses and 6-deoxy-l-hexoses under kinetic control using heterogeneous acid catalysts
  作者：Jonas J. Forsman、Reko Leino

  DOI：10.1016/j.carres.2010.05.002

  日期：2010.7

  H+ proved to be an efficient catalyst for the preparation of O-isopropylidene derivatives from a series of rare sugars. Acetonation of the reducing sugars L-arabinose, L-ribose, L-xylose, L-fucose, and L-rhamnose in N,N-dimethylformamide by 2,2-dimethoxypropane or 2-methoxypropene led to the formation of the kinetically favored di-O- and/or mono-O-isopropylidene derivatives in 46-88% yields. The method

  纤维状聚合物负载的磺酸催化剂Smopex-101 H +被证明是从一系列稀有糖中制备O-异亚丙基衍生物的有效催化剂。N，N-二甲基甲酰胺中的还原糖L-阿拉伯糖，L-核糖，L-木糖，L-岩藻糖和L-鼠李糖的乙酰化作用是由2,2-二甲氧基丙烷或2-甲氧基丙烯引起的-O-和/或单-O-异亚丙基衍生物，产率为46-88％。该方法由简单的实验程序组成，不需要预先干燥的溶剂或试剂。该催化剂易于回收并且可以再生，从而使得该方法即使对于大规模合成也在经济上可行。
• [EN] METHOD FOR PRODUCING L-FUCOSE<br/>[FR] PROCÉDÉ DE PRODUCTION DE L-FUCOSE
  申请人：GLYCOM AS

  公开号：WO2012049257A1

  公开（公告）日：2012-04-19

  The present invention provides: in a first aspect, a method for the preparation of L-fucose, wherein L-fucose precursors are produced from pectin and L-fucose is produced from the L-fucose precursors; in a second aspect, a method for the preparation of L-fucose from D-galacturonic acid or a salt thereof, wherein L-fucose precursors are produced from D-galacturonic acid or a salt thereof, and L-fucose is produced from the L-fucose precursors; and an L-fucose precursoras shown in Formula A below, wherein R is a linear or branched chain saturated hydrocarbon group with 1-6 carbon atoms, such as methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, s-butyl, t-butyl, n-hexyl, etc., preferably a methyl group.

  本发明提供：在第一方面，一种制备L-岩藻糖的方法，其中L-岩藻糖前体从果胶中产生，L-岩藻糖从L-岩藻糖前体中产生；在第二方面，一种从D-半乳糖醛酸或其盐制备L-岩藻糖的方法，其中L-岩藻糖前体从D-半乳糖醛酸或其盐中产生，L-岩藻糖从L-岩藻糖前体中产生；以及如下所示的L-岩藻糖前体，其中R是具有1-6个碳原子的线性或支链饱和碳氢化合物基团，如甲基、乙基、正丙基、异丙基、正丁基、异丁基、正丁基、叔丁基、正己基等，优选为甲基。
• De Novo Asymmetric Synthesis of Anamarine and Its Analogues
  作者：Dong Gao、George A. O'Doherty

  DOI：10.1021/jo051681p

  日期：2005.11.1

  The enantioselective synthesis of anamarine has been achieved in 21 steps. The route relies on enantio- and regioselective Sharpless dihydroxylation of dienoate ester and zinc borohydride reduction to establish the C-8-C-11 stereochemistry. A diastereoselective Leighton allylation established the desired C-5 stereochemistry. The route has also been used to prepare two diastereoisomers of anamarine in 14 steps.
• Enantioselective Synthesis of 10-<i>e</i><i>pi</i>-Anamarine via an Iterative Dihydroxylation Sequence
  作者：Dong Gao、George A. O'Doherty

  DOI：10.1021/ol047322i

  日期：2005.3.1

  The enantioselective syntheses of 10-epi-anamarine and 5,10-epi,epi-anamarine have been achieved in 13 to 14 steps. The route relies upon an enantio- and regioselective Sharpless dihydroxylation of either dienoates or trienoates to establish the C-8 to C-11 stereochemistry. A diastereoselective Leighton allylation established the desired C-5 stereochemistry. The route also relies upon a ring-closing metathesis to establish the alpha,beta-unsaturated lactones.