(S)-4-((S)-cyclohexyl(hydroxy)methyl)-2,2-dimethyl-1,3-dioxan-5-one | 182966-98-9

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (S)-4-((S)-cyclohexyl(hydroxy)methyl)-2,2-dimethyl-1,3-dioxan-5-one
• 英文别名: (1'S,4S)-4-(1'-hydroxy-1'-cyclohexyl)methyl-2,2-dimethyl-[1,3]dioxan-5-one；1,3-Dioxan-5-one, 4-[(S)-cyclohexylhydroxymethyl]-2,2-dimethyl-, (4S)-；(4S)-4-[(S)-cyclohexyl(hydroxy)methyl]-2,2-dimethyl-1,3-dioxan-5-one
• CAS: 182966-98-9
• 化学式: C₁₃H₂₂O₄
• 分子量: 242.315
• InChiKey: PSCRXHAUUNZEKD-NWDGAFQWSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.6
• 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：
  55.8
• 氢给体数：
  1
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  (S)-4-((S)-cyclohexyl(hydroxy)methyl)-2,2-dimethyl-1,3-dioxan-5-one 、 3,5-二硝基苯甲酰氯 在 4-二甲氨基吡啶 作用下， 以 二氯甲烷 为溶剂， 反应 1.0h， 生成 3,5-Dinitro-benzoic acid (S)-cyclohexyl-((S)-2,2-dimethyl-5-oxo-[1,3]dioxan-4-yl)-methyl ester
  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
• 作为产物：
  描述：

  2,2-二甲基-1,3-二恶烷-5-酮 在 二甲基十二/十四烷基叔胺 、 氯代二环己基硼烷 、 叔丁基锂 、 臭氧 、 triethylamine tris(hydrogen fluoride) 作用下， 以 四氢呋喃 、 二氯甲烷 、 苯 为溶剂， 反应 39.92h， 生成 (S)-4-((S)-cyclohexyl(hydroxy)methyl)-2,2-dimethyl-1,3-dioxan-5-one
  参考文献：
  名称：

  Highly Diastereoselective Boron-Mediated anti-Aldol Reactions of 4-Silyl Substituted 2,2-Dimethyl-1,3-dioxan-5-one. Diastereo- and Enantioselective Synthesis of Protected Oxopolyols

  摘要：

  4 硅烷化 2,2-二甲基-1,3-二氧杂环戊酮的硼烯酸盐 (S)-3 与代表性醛发生高度非对映选择性的醛醇反应，得到相应的加合物 (S,S,S)-4，收率为 78-93%，非对映异构过量 de = 96-98%。通过三乙胺-三氢氟化物络合物去除硅基，可得到受保护的氧杂环戊醇 (S,S)-5，收率为 64-79%，非对映异构体和对映体过量率为 96-98%。通过 X 射线结构分析确定了 (S,S)-5c 的绝对构型。

  DOI：

  10.1055/s-1996-4341

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。
• Direct Organocatalytic De Novo Synthesis of Carbohydrates
  作者：Dieter Enders、Christoph Grondal

  DOI：10.1002/anie.200462428

  日期：2005.2.11
• Method for the Production of a-(Alpha-Hydroxyalkyl)-1,3 Dioxan-5-Ones
  申请人：Hayat Nasir

  公开号：US20080097113A1

  公开（公告）日：2008-04-24

  A process for the synthesis of compounds of general formulas comprising the step of reacting in the presence of wherein: R=substituted or unsubstituted alkyl, aryl, heterocycles containing one or more O, N, S, P or B; R 1 and R 2 independently represent H, substituted or unsubstituted alkyl, aryl, heterocycles containing one or more O, N, S, P or B; R′═H, OH, OR or OSiX 3 , wherein X independently represent alkyl or aryl.
• US7851639B2
  申请人：——

  公开号：US7851639B2

  公开（公告）日：2010-12-14
• 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.