1,4-bis-O-tosyl-meso-erythritol | 176780-14-6

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: 1,4-bis-O-tosyl-meso-erythritol
• 英文别名: 1,4-ditosyl-meso-threitol；erythritol-1,4-ditosylate；1,4-ditosyl erythritol；[(2R,3S)-2,3-dihydroxy-4-(4-methylphenyl)sulfonyloxybutyl] 4-methylbenzenesulfonate
• CAS: 176780-14-6
• 化学式: C₁₈H₂₂O₈S₂
• 分子量: 430.5
• InChiKey: FOQGPMGPNUYCOK-HDICACEKSA-N

物化性质

• 沸点：
  657.6±55.0 °C(Predicted)
• 密度：
  1.397±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.7
• 重原子数：
  28
• 可旋转键数：
  9
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.33
• 拓扑面积：
  144
• 氢给体数：
  2
• 氢受体数：
  8

反应信息

• 作为反应物：
  描述：

  1,4-bis-O-tosyl-meso-erythritol 在 sodium sulfide 作用下， 以 乙醇 为溶剂， 反应 5.0h， 以65%的产率得到四氢噻吩二醇
  参考文献：
  名称：

  手性羟基硫杂环戊烷的合成作为羰基化合物不对称有机锌加成的潜在催化剂

  摘要：

  旋光性 3-羟基硫杂环戊烷由 L-天冬氨酸立体定向合成，氧化得到两种非对映体 S-氧化物，通过色谱分离并确定其构型。以天然(+)-(R,R)-酒石酸为原料，首次立体定向合成了C2-对称反式-(R,R)-3,4-二羟基硫杂环戊烷。还获得并表征了其一些单官能化衍生物及其 S-氧化物。以类似的方式从内消旋酒石酸中获得内消旋-顺-3,4-二羟基硫杂环戊烷，并通过脂肪酶促进的乙酰化或相应的 O,O'-二乙酰衍生物的水解进行去对称化，得到手性单乙酸酯ee 高达 36%。氧化后得到两种非对映体亚砜，通过色谱法将其分离。对晶体进行 X 射线分析，确定其绝对构型为 1S、3S、4R。所有光学活性产物都被检查为二乙基锌不对称加成到苯甲醛的潜在催化剂。然而，它们被证明具有非常低的催化活性：产物的产率在 10-90% 的范围内，但 ee 仅高达 10%。得出的结论是，在这种类型的反应中，羟基硫化物（亚砜）部分既不

  DOI：

  10.1002/hc.20076
• 作为产物：
  描述：

  1,4-ditosyl-2,3-O-isopropylidene erythritol 在 盐酸 作用下， 以 甲醇 为溶剂， 以97%的产率得到1,4-bis-O-tosyl-meso-erythritol
  参考文献：
  名称：

  手性羟基硫杂环戊烷的合成作为羰基化合物不对称有机锌加成的潜在催化剂

  摘要：

  旋光性 3-羟基硫杂环戊烷由 L-天冬氨酸立体定向合成，氧化得到两种非对映体 S-氧化物，通过色谱分离并确定其构型。以天然(+)-(R,R)-酒石酸为原料，首次立体定向合成了C2-对称反式-(R,R)-3,4-二羟基硫杂环戊烷。还获得并表征了其一些单官能化衍生物及其 S-氧化物。以类似的方式从内消旋酒石酸中获得内消旋-顺-3,4-二羟基硫杂环戊烷，并通过脂肪酶促进的乙酰化或相应的 O,O'-二乙酰衍生物的水解进行去对称化，得到手性单乙酸酯ee 高达 36%。氧化后得到两种非对映体亚砜，通过色谱法将其分离。对晶体进行 X 射线分析，确定其绝对构型为 1S、3S、4R。所有光学活性产物都被检查为二乙基锌不对称加成到苯甲醛的潜在催化剂。然而，它们被证明具有非常低的催化活性：产物的产率在 10-90% 的范围内，但 ee 仅高达 10%。得出的结论是，在这种类型的反应中，羟基硫化物（亚砜）部分既不

  DOI：

  10.1002/hc.20076

文献信息

• The Stereoisomeric Diaminobutanediol and Dioxadiazadecalin Systems: Synthesis, Structure, Stereoelectronics, and Conformation – Theory vs. Experiment
  作者：Alexander Star、Israel Goldberg、N. Gabriel Lemcoff、Benzion Fuchs

  DOI：10.1002/(sici)1099-0690(199909)1999:9<2033::aid-ejoc2033>3.0.co;2-k

  日期：1999.9

  We present new approaches to the (C2) chiral and meso 1,4-diamino-2,3-butanediol (1) and 2,3-diamino-1,4-butanediol (2) and derivatives. Reactions of these compounds with aldehydes to form the novel 1,5-dioxa-3,7-diazadecalin (DODAD) and 1,5-diaza-3,7-dioxadecalin (DADOD) classes of compounds (7, 9, 11–15) are also reported. These reactions are diastereospecific, i.e., erythro (meso) or threostarting

  我们提出了 (C2) 手性和内消旋 1,4-二氨基-2,3-丁二醇 (1) 和 2,3-二氨基-1,4-丁二醇 (2) 及其衍生物的新方法。这些化合物与醛反应形成新型 1,5-二氧杂-3,7-二氮杂萘 (DODAD) 和 1,5-二氮杂-3,7-二恶烷 (DADOD) 类化合物 (7, 9, 11–15) ) 也有报道。这些反应是非对映特异性的，即赤型（内消旋）或苏型起始化合物分别产生反式或顺式产物。这些系统的结构、构象和立体电子方面通过实验和计算进行了探索，并提供了对它们的特性和行为的深入了解。在 X 射线、NMR 和反式 DODAD (14) 和反式 DADOD (15) 的 N,N'-二苄基衍生物的计算结果之间观察到良好的一致性。
• Interstrand and Intrastrand DNA−DNA Cross-Linking by 1,2,3,4-Diepoxybutane:  Role of Stereochemistry
  作者：Soobong Park、Christopher Anderson、Rachel Loeber、Mahadevan Seetharaman、Roger Jones、Natalia Tretyakova

  DOI：10.1021/ja051979x

  日期：2005.10.1

  1,2,3,4-Diepoxybutane (DEB) is a bifunctional electrophile capable of forming DNA-DNA and DNA-protein cross-links. DNA alkylation by DEB produces N7-(2'-hydroxy-3',4'-epoxybut-1'-yl)-guanine monoadducts, which can then form 1,4-bis-(guan-7-yl)-2,3-butanediol (bis-N7G-BD) lesions. All three optical isomers of DEB are produced metabolically from 1,3-butadiene, but S,S-DEB is the most cytotoxic and genotoxic. In the present work, interstrand and intrastrand DNA-DNA cross-linking by individual DEB stereoisomers was investigated by PAGE, mass spectrometry, and stable isotope labeling. S,S-, R,R-, and meso-diepoxides were synthesized from L-dimethyl-2,3-O-isopropylidene-tartrate, D-dimethyl-2,3-O-isopropyl id e ne-tart rate, and meso-erythritol, respectively. Total numbers of bis-N7G-BD lesions (intrastrand and interstrand) in calf thymus DNA treated separately with S,S-, R,R-, or meso-DEB (0.01-0.5 mM) were similar as determined by capillary HPLC-ESI+-MS/MS of DNA hydrolysates. However, denaturing PAGE has revealed that S,S-DEB produced the highest number of interchain cross-links in 5'-GGC-3/3'-CCG-5' sequences. Intrastrand adduct formation by DEB was investigated by a novel methodology based on stable isotope labeling HPLC-ESI+-MS/MS. Meso DEB treatment of DNA duplexes containing 5'-[1,7,NH2-N-15(3),2-C-13-G]GC-3'/3'-CCG-5' and 5'-GGC-3/3'-CC[N-15(3),2-C-13-G]-5' trinucleotides gave rise to comparable numbers of 12-intrastrand and 1,3-interstrand bis-N7G-BD cross-links, while S,S DEB produced few intrastrand lesions. R,P-DEB treated DNA contained mostly 1,3-interstrand bis-N7G-BD, along with smaller amounts of 1,2-interstrand and 1,2-intrastrand adducts. The effects of DEB stereochemistry on its ability to form DNA-DNA cross-links may be rationalized by the spatial relationships between the epoxy alcohol side chains in stereoisomeric N7-(2'-hydroxy-3',4'-epoxybut-1'-yl)-guanine adclucts and their DNA environment. Different cross-linking specificities of DEB stereoisomers provide a likely structural basis for their distinct biological activities.
• MULTIGRAM-SCALE STEREOSELECTIVE SYNTHESIS OF<i>MESO</i>-1,3-BUTADIENE BISEPOXIDE
  作者：David J. Claffey

  DOI：10.1081/scc-120012996

  日期：2002.1

  meso-1,3-Butadiene bisepoxide, a potential building block for natural product synthesis and of interest as a toxic metabolite of butadiene, was synthesized in multi-gram scale in two steps from meso-erythritol in good overall yield.
• Stereodependent Fusion and Fission of Vesicles:  Calcium Binding of Synthetic Gemini Phospholipids Containing Two Phosphate Groups
  作者：N. A. J. M. Sommerdijk、T. H. L. Hoeks、M. Synak、M. C. Feiters、R. J. M. Nolte、B. Zwanenburg

  DOI：10.1021/ja962303s

  日期：1997.5.1

  Three different stereoisomers of a phosphatidic acid analog bearing two phosphate groups have been synthesized from tartaric acid and erythritol. The obtained diastereomeric gemini surfactants differ in their aggregation behavior due to the different spatial orientations of their functional groups. The most remarkable difference in aggregation behavior is encountered when calcium ions are added to vesicle suspensions of the respective isomers. The vesicles formed from the (S,S) and (R,R) isomer undergo fusion, whereas those of the (R,S) isomer show vesicle fission. This remarkable behavior can be explained by a change in the molecular packing of the lipid molecules upon the complexation with calcium ions. An analysis of physical data obtained prior to and after the addition of the calcium ions reveals that the head groups of the diastereomeric surfactants respond differently to these ions: those of the (S,S) isomer increase in size, whereas those of the (R,S) isomer decrease in size. This phenomenon accounts for occurrence of fusion and fission of the vesicles, respectively.
• Synthesis of chiral hydroxythiolanes as potential catalysts for asymmetric organozinc additions to carbonyl compounds
  作者：Piotr Kie?basi?ski、Ma?gorzata Albrycht、Marian Miko?ajczyk、Micha? W. Wieczorek、Wies?aw R. Majzner、Agnieszka Filipczak、Piotr Cio?kiewicz

  DOI：10.1002/hc.20076

  日期：——

  give a chiral monoacetate with ee up to 36%. After its oxidation two diastereomeric sulfoxides were obtained which were separated by chromatography. The crystalline one was subjected to X-ray analysis and its absolute configuration was determined as 1S, 3S, 4R. All the optically active products were checked as potential catalysts for asymmetric addition of diethylzinc to benzaldehyde. However, they

  旋光性 3-羟基硫杂环戊烷由 L-天冬氨酸立体定向合成，氧化得到两种非对映体 S-氧化物，通过色谱分离并确定其构型。以天然(+)-(R,R)-酒石酸为原料，首次立体定向合成了C2-对称反式-(R,R)-3,4-二羟基硫杂环戊烷。还获得并表征了其一些单官能化衍生物及其 S-氧化物。以类似的方式从内消旋酒石酸中获得内消旋-顺-3,4-二羟基硫杂环戊烷，并通过脂肪酶促进的乙酰化或相应的 O,O'-二乙酰衍生物的水解进行去对称化，得到手性单乙酸酯ee 高达 36%。氧化后得到两种非对映体亚砜，通过色谱法将其分离。对晶体进行 X 射线分析，确定其绝对构型为 1S、3S、4R。所有光学活性产物都被检查为二乙基锌不对称加成到苯甲醛的潜在催化剂。然而，它们被证明具有非常低的催化活性：产物的产率在 10-90% 的范围内，但 ee 仅高达 10%。得出的结论是，在这种类型的反应中，羟基硫化物（亚砜）部分既不