(S)-4-((R)-1-(tert-butyldimethylsilyloxy)-2,2-dimethoxyethyl)-2,2-dimethyl-1,3-dioxan-5-one | 875903-76-7

• 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-(tert-butyldimethylsilyloxy)-2,2-dimethoxyethyl)-2,2-dimethyl-1,3-dioxan-5-one
• 英文别名: (4S)-4-[(1R)-1-[tert-butyl(dimethyl)silyl]oxy-2,2-dimethoxyethyl]-2,2-dimethyl-1,3-dioxan-5-one
• CAS: 875903-76-7
• 化学式: C₁₆H₃₂O₆Si
• 分子量: 348.512
• InChiKey: QITVMHIGINNVLY-CHWSQXEVSA-N

物化性质

• 沸点：
  357.2±42.0 °C(predicted)
• 密度：
  1.006±0.06 g/cm3(Temp: 20 °C; Press: 760 Torr)(predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.72
• 重原子数：
  23
• 可旋转键数：
  7
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.94
• 拓扑面积：
  63.2
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  (S)-4-((R)-1-(tert-butyldimethylsilyloxy)-2,2-dimethoxyethyl)-2,2-dimethyl-1,3-dioxan-5-one 在 L-Selectride 作用下， 以 四氢呋喃 、 正己烷 为溶剂， 以79%的产率得到3,5-O-isopropylidene-4-O-tert-butyldimethylsilyl-L-lyxose dimethyl acetal
  参考文献：
  名称：

  迈向鼠疫耶尔森菌细胞壁多糖的合成：L-甘油-D-甘露聚糖-庚糖结构单元的对映选择性合成。

  摘要：

  描述了用于鼠疫耶尔森氏菌细胞壁多糖的全合成的L-甘油-D-甘露聚糖-庚基结构单元的短且对映选择性的从头合成。

  DOI：

  10.1039/c000784f
• 作为产物：
  描述：

  2,2-二甲基-1,3-二恶烷-5-酮 在 咪唑 、 L-脯氨酸 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 反应 96.0h， 生成 (S)-4-((R)-1-(tert-butyldimethylsilyloxy)-2,2-dimethoxyethyl)-2,2-dimethyl-1,3-dioxan-5-one
  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

• Building Higher Carbohydrates via Dioxanone Aldol Chemistry: The α,α′-Bisaldol Approach
  作者：Izabella Niewczas、Marek Majewski

  DOI：10.1002/ejoc.200800844

  日期：——

  A synthetic approach to higher carbohydrates via the sequence of two aldol reactions that proceed at the α and α′ positions of 2,2-dimethyl-1,3-dioxan-5-one (dioxanone) is described. As reported before, the first aldol reaction works well under organocatalytic conditions (proline catalysis), this is followed by protection of the hydroxy, deprotonation of the resulting compound using excess of LDA,

  描述了通过在 2,2-二甲基-1,3-二恶烷-5-one（二恶烷酮）的 α 和 α' 位置进行的两个羟醛反应序列合成高级碳水化合物的方法。如前所述，第一个羟醛反应在有机催化条件下（脯氨酸催化）运行良好，然后是保护羟基，使用过量的 LDA 使所得化合物去质子化，以及第二个羟醛添加。这一系列反应产生了具有直链碳骨架的化合物，每个碳上都有一个基于氧的官能团。大多数组都受到保护。6-C-苯基-D-甘油-D-allo-己基吡喃糖和D-赤型-D-allooctopyranose 的短合成说明了该策略的效用（© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany , 2009)
• 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。
• 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。
• Stereodivergent Synthesis of d,d- and l,l-glycero-β-allo-Heptopyranoses on a Dioxanone Scaffold
  作者：Marek Majewski、Nagarjuna Palyam、Izabella Niewczas

  DOI：10.1055/s-0032-1290461

  日期：——

  We report a stereodivergent synthesis of both enantiomers of glycero-allo-heptose from 2,2-dimethyl-1,3-dioxan-5-one, a readily available nonchiral scaffold, and from two different synthetic equivalents of glyoxal: dimethoxyacetaldehyde and 1,3-dithiane-2-carboxaldehyde. The short synthetic sequence involves first a proline-mediated, and then a lithium enolate mediated aldol reaction at the alpha-and alpha'-positions of the dioxanone ring, respectively, and demonstrates the complementary nature of organocatalysis and metal enolate based methods.
• 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.