(S)-4-((R)-[1,3]Dithian-2-yl-hydroxy-methyl)-2,2-dimethyl-[1,3]dioxan-5-one | 875903-72-3

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (S)-4-((R)-[1,3]Dithian-2-yl-hydroxy-methyl)-2,2-dimethyl-[1,3]dioxan-5-one
• 英文别名: (4S)-4-[(R)-1,3-dithian-2-yl(hydroxy)methyl]-2,2-dimethyl-1,3-dioxan-5-one
• CAS: 875903-72-3
• 化学式: C₁₁H₁₈O₄S₂
• 分子量: 278.394
• InChiKey: HEJUMPSXWUXINR-RKDXNWHRSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.9
• 重原子数：
  17
• 可旋转键数：
  2
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.91
• 拓扑面积：
  106
• 氢给体数：
  1
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  (S)-4-((R)-[1,3]Dithian-2-yl-hydroxy-methyl)-2,2-dimethyl-[1,3]dioxan-5-one 在 三乙酰氧基硼氢化钠 作用下， 以 二氯甲烷 、 溶剂黄146 为溶剂， 反应 24.0h， 生成 (4R,5R)-4-[(R)-1,3-dithian-2-yl(hydroxy)methyl]-2,2-dimethyl-1,3-dioxan-5-ol
  参考文献：
  名称：

  Building carbohydrates on the dioxanone scaffold: stereoselective synthesis of d-glycero-d-manno-2-octulose

  摘要：

  The title compound has been synthesized via two proline-catalyzed aldol addition reactions of 2,2-dialkyl-1,3-dioxan-5ones: the first addition to 1,3-dithiane-2-carboxaldehyde, followed by reduction to the corresponding diol, protection of the OH groups and dithiane hydrolysis afforded a protected D-ribose that was used in the second aldol addition reaction. (c) 2007 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetlet.2007.10.100
• 作为产物：
  描述：

  2,2-二甲基-1,3-二恶烷-5-酮 、 1,3-二噻烷-2-甲醛 在 L-脯氨酸 、 lithium chloride 作用下， 以 二甲基亚砜 为溶剂， 反应 48.0h， 生成 (S)-4-((R)-[1,3]Dithian-2-yl-hydroxy-methyl)-2,2-dimethyl-[1,3]dioxan-5-one
  参考文献：
  名称：

  Building carbohydrates on the dioxanone scaffold: stereoselective synthesis of d-glycero-d-manno-2-octulose

  摘要：

  The title compound has been synthesized via two proline-catalyzed aldol addition reactions of 2,2-dialkyl-1,3-dioxan-5ones: the first addition to 1,3-dithiane-2-carboxaldehyde, followed by reduction to the corresponding diol, protection of the OH groups and dithiane hydrolysis afforded a protected D-ribose that was used in the second aldol addition reaction. (c) 2007 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetlet.2007.10.100

文献信息

• Acids as Proline Co-catalysts in the Aldol Reaction of 1,3-Dioxan-5-ones
  作者：Marek Majewski、Izabella Niewczas、Nagarjuna Palyam

  DOI：10.1055/s-2006-950421

  日期：2006.9

  Proline-catalyzed aldol addition of 2,2-dialkyl-1,3-dioxan-5-ones to aldehydes requires the presence of water, pyridinium p-toluenesulfonate or lithium chloride to proceed with high yield and high enantioselectivity. Acyclic amino acids such as alanine, phenylalanine, lysine and valine also catalyze the reaction but overall show yields and selectivities inferior to those of proline. An ester of a proline analogue shows catalytic activity in the presence of PPTS, suggesting that, in the presence of a Brønsted acid, a free ­carboxyl group on the catalyst might not be critical.

  脯氨酸催化的 2,2-二烷基-1,3-二噁烷-5-酮与醛的醇醛加成反应需要水、对甲苯磺酸吡啶盐或氯化锂的存在，以实现高产率和高对映体选择性。非环状氨基酸，如丙氨酸、苯丙氨酸、赖氨酸和缬氨酸也能催化该反应，但总体产率和选择性逊色于脯氨酸。在存在 PPTS 的条件下，脯氨酸类似物的酯显示出催化活性，这表明在 Brønsted 酸的存在下，催化剂上的自由羧基可能并非关键。
• Direct asymmetric organocatalytic de novo synthesis of carbohydrates
  作者：Christoph Grondal、Dieter Enders

  DOI：10.1016/j.tet.2005.09.060

  日期：2006.1

  A biomimetic organocatalytic asymmetric synthesis of carbohydrates can be accomplished by a proline catalyzed aldol reaction with the dihydroxyacetone equivalent 2,2-dimethyl-1,3-dioxan-5-one and various aldehydes. The biomimetic C3+Cn strategy directly generates selectively protected carbohydrates in one step, which can be easily deprotected. Additionally, the stereoselective reduction of the keto

  碳水化合物的仿生有机催化不对称合成可以通过脯氨酸催化的羟醛反应与二羟基丙酮当量的2,2-二甲基-1,3-二恶烷-5-酮和各种醛反应来完成。仿生C 3 + C n策略可在一个步骤中直接生成选择性保护的碳水化合物，可以很容易地对其进行脱保护。另外，酮基功能的立体选择性降低允许直接进入不同的醛糖。
• Building carbohydrates on the dioxanone scaffold: stereoselective synthesis of d-glycero-d-manno-2-octulose
  作者：Nagarjuna Palyam、Izabella Niewczas、Marek Majewski

  DOI：10.1016/j.tetlet.2007.10.100

  日期：2007.12

  The title compound has been synthesized via two proline-catalyzed aldol addition reactions of 2,2-dialkyl-1,3-dioxan-5ones: the first addition to 1,3-dithiane-2-carboxaldehyde, followed by reduction to the corresponding diol, protection of the OH groups and dithiane hydrolysis afforded a protected D-ribose that was used in the second aldol addition reaction. (c) 2007 Elsevier Ltd. All rights reserved.