(4R,5S)-4-((R)-1-(tert-butyldimethylsilyloxy)-2,2-dimethoxyethyl)-2,2-dimethyl-1,3-dioxan-5-ol | 875903-77-8

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (4R,5S)-4-((R)-1-(tert-butyldimethylsilyloxy)-2,2-dimethoxyethyl)-2,2-dimethyl-1,3-dioxan-5-ol
• 英文别名: (4R,5S)-4-[(1R)-1-[tert-butyl(dimethyl)silyl]oxy-2,2-dimethoxyethyl]-2,2-dimethyl-1,3-dioxan-5-ol
• CAS: 875903-77-8
• 化学式: C₁₆H₃₄O₆Si
• 分子量: 350.528
• InChiKey: BROJUQGFXUGFJK-YNEHKIRRSA-N

物化性质

• 沸点：
  367.2±37.0 °C(predicted)
• 密度：
  1.010±0.06 g/cm3(Temp: 20 °C; Press: 760 Torr)(predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.51
• 重原子数：
  23
• 可旋转键数：
  7
• 环数：
  1.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  66.4
• 氢给体数：
  1
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  (4R,5S)-4-((R)-1-(tert-butyldimethylsilyloxy)-2,2-dimethoxyethyl)-2,2-dimethyl-1,3-dioxan-5-ol 在 2,6-二甲基吡啶 、 三氟甲磺酸三甲基硅酯 作用下， 以 二氯甲烷 为溶剂， 反应 1.5h， 以51%的产率得到
  参考文献：
  名称：

  直接有机催化进入选择性保护的戊糖和衍生物

  摘要：

  根据仿生C 3 + C n从头合成碳水化合物的策略，将脯氨酸催化的2,2-二甲基-1,3-二恶烷-5-酮与二甲氧基乙醛的羟醛反应作为关键反应。根据Whitesides转化策略，采用受保护的D-赤型-戊基-4-戊糖（de > 96％，ee = 94％）快速和分散地进入各种选择性和部分正交的受保护的醛糖及其衍生物，如氨基糖。 ，硫代糖，脱氧糖，4- C取代的（烷基化的）醛糖和环氧糖。

  DOI：

  10.1002/adsc.200600573
• 作为产物：
  描述：

  (4S,1'R)-4-(1'-hydroxy-2',2'-dimethoxyethyl)-2,2-dimethyl-1,3-dioxan-5-one 在 咪唑 、 L-Selectride 作用下， 以 四氢呋喃 、 N,N-二甲基甲酰胺 为溶剂， 反应 24.0h， 生成 (4R,5S)-4-((R)-1-(tert-butyldimethylsilyloxy)-2,2-dimethoxyethyl)-2,2-dimethyl-1,3-dioxan-5-ol
  参考文献：
  名称：

  Dihydroxyacetone Variants in the Organocatalytic Construction of Carbohydrates:  Mimicking Tagatose and Fuculose Aldolases

  摘要：

  Dihydroxyacetone variants have been explored as donors in organocatalytic aldol reactions with various aldehyde and ketone acceptors. The protected form of dihydroxyacetone that was chosen for in-depth study was 2,2-dimethyl-1,3-dioxan-5-one, 1. Among the catalysts surveyed here, proline proved to be superior in terms of yield and stereoselectivities in the construction of various carbohydrate scaffolds. In a fashion analogous to aldolase enzymes, the de novo preparation of L-ribulose, L-lyxose, D-ribose, D-tagatose, 1-amino-1-deoxy-D-lyxitol, and other carbohydrates was accomplished via the use of 1 and proline. In reactions using 2,2-dimethyl-1,3-dioxan-5-one 1 as a donor, (S)-proline can be used as a functional mimic of tagatose aldolase, whereas (R)-proline can be regarded as an organocatalytic mimic of fuculose aldolase.

  DOI：

  10.1021/jo0602017

文献信息

• 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。
• Dihydroxyacetone Variants in the Organocatalytic Construction of Carbohydrates:  Mimicking Tagatose and Fuculose Aldolases
  作者：Jeff T. Suri、Susumu Mitsumori、Klaus Albertshofer、Fujie Tanaka、Carlos F. Barbas

  DOI：10.1021/jo0602017

  日期：2006.5.1

  Dihydroxyacetone variants have been explored as donors in organocatalytic aldol reactions with various aldehyde and ketone acceptors. The protected form of dihydroxyacetone that was chosen for in-depth study was 2,2-dimethyl-1,3-dioxan-5-one, 1. Among the catalysts surveyed here, proline proved to be superior in terms of yield and stereoselectivities in the construction of various carbohydrate scaffolds. In a fashion analogous to aldolase enzymes, the de novo preparation of L-ribulose, L-lyxose, D-ribose, D-tagatose, 1-amino-1-deoxy-D-lyxitol, and other carbohydrates was accomplished via the use of 1 and proline. In reactions using 2,2-dimethyl-1,3-dioxan-5-one 1 as a donor, (S)-proline can be used as a functional mimic of tagatose aldolase, whereas (R)-proline can be regarded as an organocatalytic mimic of fuculose aldolase.
• A Direct Organocatalytic Entry to Selectively Protected Aldopentoses and Derivatives
  作者：Christoph Grondal、Dieter Enders

  DOI：10.1002/adsc.200600573

  日期：2007.3.5

  The proline-catalysed aldol reaction of 2,2-dimethyl-1,3-dioxan-5-one with dimethoxyacetaldehyde is used as the key reaction according to the biomimetic C3+Cn strategy for de novo carbohydrate synthesis. Based on the Whitesides inversion strategy, protected D-erythro-pentos-4-ulose (de>96 %, ee=94 %) was employed for a rapid and divergent entry to various selectively and partly orthogonal protected

  根据仿生C 3 + C n从头合成碳水化合物的策略，将脯氨酸催化的2,2-二甲基-1,3-二恶烷-5-酮与二甲氧基乙醛的羟醛反应作为关键反应。根据Whitesides转化策略，采用受保护的D-赤型-戊基-4-戊糖（de > 96％，ee = 94％）快速和分散地进入各种选择性和部分正交的受保护的醛糖及其衍生物，如氨基糖。 ，硫代糖，脱氧糖，4- C取代的（烷基化的）醛糖和环氧糖。