5,6-O-isopropylidene-1-deoxy-D-sorbose | 64513-21-9

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 5,6-O-isopropylidene-1-deoxy-D-sorbose
• 英文别名: 1-Desoxy-5,6-isopropyliden-D-arabino/xylo-hexulose；(3R,4R)-4-[(4R)-2,2-dimethyl-1,3-dioxolan-4-yl]-3,4-dihydroxybutan-2-one
• CAS: 64513-21-9
• 化学式: C₉H₁₆O₅
• 分子量: 204.223
• InChiKey: YDRFIUZGMJJXOA-CSMHCCOUSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  -1
• 重原子数：
  14
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.89
• 拓扑面积：
  76
• 氢给体数：
  2
• 氢受体数：
  5

反应信息

• 作为产物：
  描述：

  羟基丙酮 、 (R)-(+)-2,2-二甲基-1,3-二氧戊环-4-甲醛 在 (2S,2'S)-N,N'-((1S,2S)-1,2-diphenylethane-1,2-diyl)bis(2-amino-3-((tertbutyldiphenylsilyl)oxy)propanamide) 作用下， 以 四氢呋喃 、 水 为溶剂， 反应 24.0h， 以37%的产率得到5,6-O-isopropylidene-1-deoxy-D-sorbose
  参考文献：
  名称：

  Amine-Catalyzed Direct Aldol Reactions of Hydroxy- and Dihydroxyacetone: Biomimetic Synthesis of Carbohydrates

  摘要：

  This article presents comprehensive studies on the application of primary, secondary, and tertiary amines as efficient organocatalysts for the de novo synthesis of ketoses and deoxyketoses. Mimicking the actions of aldolase enzymes, the synthesis of selected carbohydrates was accomplished in aqueous media by using proline- and serine-based organocatalysts. The presented methodology also provides direct access to unnatural L-carbohydrates from the (S)-glyceraldehyde precursor. Determination of the absolute configuration of all obtained sugars was feasible using a methodology consisting of concerted ECD and VCD spectroscopy.

  DOI：

  10.1021/jo500860g

文献信息

• Amino Acid Catalyzed Direct Asymmetric Aldol Reactions:  A Bioorganic Approach to Catalytic Asymmetric Carbon−Carbon Bond-Forming Reactions
  作者：Kandasamy Sakthivel、Wolfgang Notz、Tommy Bui、Carlos F. Barbas

  DOI：10.1021/ja010037z

  日期：2001.6.1

  lack of nonlinear effects. The reactions tolerate a small amount of water (<4 vol %), do not require inert reaction conditions and preformed enolate equivalents, and can be conveniently performed at room temperature in various solvents. In addition, reaction conditions that facilitate catalyst recovery as well as immobilization are described. Finally, mechanistically related addition reactions such as

  使用醛和未改性的酮以及市售的手性环状仲胺作为催化剂，已经成功地进行了直接不对称催化醛醇反应。基于结构的催化剂筛选确定 L-脯氨酸和 5,5-二甲基噻唑烷 4-羧酸盐 (DMTC) 是最强大的氨基酸催化剂，可用于作为醛醇供体的无环酮和环状酮与芳香族和脂肪族醛反应，得到相应的醛醇产物具有高区域选择性、非对映选择性和对映选择性。使用羟基丙酮作为羟醛供体的反应提供了作为主要产物的抗 1,2-二醇，其 ee 值高达 >99%。假设反应通过无金属的 Zimmerman-Traxler 型过渡态进行，并涉及烯胺中间体。观察到的产物立体化学与提议的过渡态一致。非线性效应的缺乏提供了进一步的支持证据。该反应耐受少量水（<4 vol%），不需要惰性反应条件和预先形成的烯醇当量，并且可以在室温下在各种溶剂中方便地进行。此外，还描述了促进催化剂回收和固定的反应条件。最后，还开发了与机械相关的加成反应，例如酮加成到亚胺（曼尼希型反应）和硝基烯烃和
• Amine-Catalyzed Direct Aldol Reactions of Hydroxy- and Dihydroxyacetone: Biomimetic Synthesis of Carbohydrates
  作者：Oskar Popik、Monika Pasternak-Suder、Katarzyna Leśniak、Magdalena Jawiczuk、Marcin Górecki、Jadwiga Frelek、Jacek Mlynarski

  DOI：10.1021/jo500860g

  日期：2014.6.20

  This article presents comprehensive studies on the application of primary, secondary, and tertiary amines as efficient organocatalysts for the de novo synthesis of ketoses and deoxyketoses. Mimicking the actions of aldolase enzymes, the synthesis of selected carbohydrates was accomplished in aqueous media by using proline- and serine-based organocatalysts. The presented methodology also provides direct access to unnatural L-carbohydrates from the (S)-glyceraldehyde precursor. Determination of the absolute configuration of all obtained sugars was feasible using a methodology consisting of concerted ECD and VCD spectroscopy.