3,4-O-isopropylidene-6-O-tert-butyldiphenylsilyl-D-galactal | 137792-66-6

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 二氧吡喃
• 英文名称: 3,4-O-isopropylidene-6-O-tert-butyldiphenylsilyl-D-galactal
• 英文别名: 6-O-(tert-butyldiphenylsilyl)-3,4-O-isopropylidene-D-galactal；tert-Butyl(((3aR,4R,7aR)-2,2-dimethyl-3a,7a-dihydro-4H-[1,3]dioxolo[4,5-c]pyran-4-yl)methoxy)diphenylsilane；[(3aR,4R,7aR)-2,2-dimethyl-4,7a-dihydro-3aH-[1,3]dioxolo[4,5-c]pyran-4-yl]methoxy-tert-butyl-diphenylsilane
• CAS: 137792-66-6
• 化学式: C₂₅H₃₂O₄Si
• 分子量: 424.612
• InChiKey: DILLXPKGHGGSCI-DNVJHFABSA-N

物化性质

• 沸点：
  476.7±45.0 °C(Predicted)
• 密度：
  1.11±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4.0
• 重原子数：
  30
• 可旋转键数：
  6
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.44
• 拓扑面积：
  36.9
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  3,4-O-isopropylidene-6-O-tert-butyldiphenylsilyl-D-galactal 在 N-碘代丁二酰亚胺 、 4 A molecular sieve 、 四丁基氟化铵 、 sodium hydride 、 pyridinium chlorochromate 作用下， 以 四氢呋喃 、 二氯甲烷 、 乙腈 为溶剂， 反应 6.25h， 生成 Ethyl (Methyl 2,6,7-trideoxy-2-iodo-3,4-isopropylidene-β-D-galacto-oct-6(E)-eno-1,5-pyranosid)uronate
  参考文献：
  名称：

  Radical cyclization routes to bridged pyranosides as precursors of densely functionalized cycloalkanes

  摘要：

  Glycals derived from hexopyranoses permit the incorporation of iodine at C-2 as well as elaboration of an olefinic residue via the C-5-hydroxymethyl group. Radical cyclization of these functionalities leads to bicyclic systems whose bridge sizes depend on the lengths of the olefinic appendages. Hydrolysis of the anomeric centers of the [2.2.1] structures leads spontaneously to cyclopentane derivatives. However, with [2.2.2] structures, the hemiacetal intermediates are stable in bicyclic forms but are opened readily upon mcerpatolysis with propane dithiol to give cyclohexane derivatives.

  DOI：

  10.1021/jo00028a033
• 作为产物：
  描述：

  (2R,3R,4R)-2-(羟基甲基)-3,4-二氢-2H-吡喃-3,4-二醇 在 咪唑 、 4-甲基苯磺酸吡啶 作用下， 以 四氢呋喃 、 二氯甲烷 为溶剂， 反应 5.0h， 生成 3,4-O-isopropylidene-6-O-tert-butyldiphenylsilyl-D-galactal
  参考文献：
  名称：

  Radical cyclization routes to bridged pyranosides as precursors of densely functionalized cycloalkanes

  摘要：

  Glycals derived from hexopyranoses permit the incorporation of iodine at C-2 as well as elaboration of an olefinic residue via the C-5-hydroxymethyl group. Radical cyclization of these functionalities leads to bicyclic systems whose bridge sizes depend on the lengths of the olefinic appendages. Hydrolysis of the anomeric centers of the [2.2.1] structures leads spontaneously to cyclopentane derivatives. However, with [2.2.2] structures, the hemiacetal intermediates are stable in bicyclic forms but are opened readily upon mcerpatolysis with propane dithiol to give cyclohexane derivatives.

  DOI：

  10.1021/jo00028a033

文献信息

• Stereocontrolled Synthesis of 2-Deoxy-galactopyranosides via Isopropylidene-Protected 6-<i>O</i>-Silylated Donors
  作者：Dan-Mei Yang、Yue Chen、Ryan P. Sweeney、Todd L. Lowary、Xing-Yong Liang

  DOI：10.1021/acs.orglett.8b00632

  日期：2018.4.20

  The stereocontrolled synthesis of 2-deoxy-d-arabino-hexopyranosides (“galactopyranosides”) using 3,4-O-isopropylidene-6-O-tert-butyldiphenylsilyl-protected glycosyl donors is reported. 2-Deoxy-thioglycoside 3e gives excellent α-selectivity, while galactal 9 leads to, in a two-step protocol, 2-deoxy-β-glycosides in high stereoselectivity. The selectivity of both reagents is believed to arise from the

  2-脱氧的立体控制合成d -阿拉伯-hexopyranosides使用3,4-（“吡喃半乳糖苷”）ö异亚丙基-6- ø -叔报道-butyldiphenylsilyl保护的糖基供体。2-脱氧-硫代糖苷3e具有出色的α-选择性，而半乳糖9在两步操作中可产生高立体选择性的2-脱氧-β-糖苷。据信两种试剂的选择性是由跨越O-3和O-4的异亚丙基缩醛与O-6上的空间上需要的甲硅烷基基团的组合产生的。该方法的实用性通过合成含有2-deoxyα-和β- d的三糖来证明-半乳糖吡喃糖基残基。
• Umpolung Reactivity in the Stereoselective Synthesis of S-Linked 2-Deoxyglycosides
  作者：Kedar N. Baryal、Danyang Zhu、Xiaohua Li、Jianglong Zhu

  DOI：10.1002/anie.201301682

  日期：2013.7.29

  Take control! An unprecedented sulfenylation of stereochemically defined 2‐deoxyglycosyl lithium species with asymmetric sugar‐derived disulfide acceptors enabled the stereoselective synthesis of both α‐ and β‐S‐linked 2‐deoxyoligosaccharides. Reductive lithiation of 2‐deoxyglycosyl phenylsulfides at −78 °C provides predominantly axial glycosyl lithium species, which upon warming isomerize to predominantly

  控制住！立体化学定义的2-脱氧糖基锂物种与不对称糖衍生的二硫键受体的前所未有的亚磺酰化作用，使得立体选择性合成α-和β-S-连接的2-脱氧寡糖成为可能。在−78°C下2-脱氧糖基苯基硫化物的还原锂化作用主要提供了轴向糖基锂物质，该物质在升温时异构化为主要为赤道的锂物质（请参见方案）。
• Use of acid-labile protective groups for carbohydrate moieties in synthesis of glycopeptides related to type II collagen
  作者：Johan Broddefalk、Karl-Erik Bergquist、Jan Kihlberg

  DOI：10.1016/s0040-4020(98)83057-3

  日期：1998.9

  silyl, isopropylidene and 4-methoxybenzyl protective groups have been attached to the amino acid 5-hydroxy-L-norvaline. The resulting glycosylated building blocks were used in Fmoc solid-phase synthesis of glycopeptides related to a fragment from type II collagen which is immunodominant in a mouse model for rheumatoid arthritis. The protective groups used for the carbohydrate moieties were completely removed

  带有甲硅烷基，异亚丙基和4-甲氧基苄基保护基的β-D-半乳糖吡喃糖基和α-D-吡喃葡萄糖基-β-D-吡喃半乳糖基已连接到氨基酸5-羟基-L-正缬氨酸上。所得的糖基化结构单元用于与II型胶原蛋白片段相关的糖肽的Fmoc固相合成，该片段在类风湿性关节炎小鼠模型中具有免疫优势。在使O-糖苷键保持完整的条件下，在固相进行酸催化的糖肽裂解过程中，用于碳水化合物部分的保护基被完全除去。
• Synthesis of Oxime-Linked Mucin Mimics Containing the Tumor-Related T_N and Sialyl T_N Antigens
  作者：Lisa A. Marcaurelle、Youngsook Shin、Scarlett Goon、Carolyn R. Bertozzi

  DOI：10.1021/ol0166247

  日期：2001.11.1

  [reaction--see text] The synthesis of oxime-linked mucin mimics was accomplished via the incorporation of multiple ketone residues into a peptide followed by reaction with aminooxy sugars corresponding to the tumor-related T(N) and sialyl T(N) (ST(N)) antigens.

  [反应-见正文]肟连接的粘蛋白模拟物的合成是通过将多个酮残基掺入肽中，然后与对应于肿瘤相关T（N）和唾液酸T（N）的氨氧基糖反应完成的（ ST（N））抗原。
• 一种β-2-脱氧糖苷键的立体选择性合成的方法
  申请人：四川轻化工大学

  公开号：CN109912642A

  公开（公告）日：2019-06-21

  本发明公开了一种β‑2‑脱氧糖苷键的立体选择性合成的方法，以3,4‑O‑异亚丙基‑6‑O‑叔丁基二苯基甲硅烷基‑D‑半乳糖烯为供体，与糖基受体和分子筛在促进剂存在条件下，进行糖苷化反应。其中，3,4‑O‑异亚丙基‑6‑O‑叔丁基二苯基甲硅烷基‑D‑半乳糖烯在3‑位和4‑位羟基上安装异亚丙基缩醛基保护基和在6‑位羟基上安装叔丁基二苯基硅基(TBDPS)保护基，通过上述保护基的协同作用，控制供体的糖环构象，实现β‑构型高立体选择性的合成。该方法可以有效高选择性控制糖苷化反应的立体选择性，底物适用范围广，操作方便，原料易得，糖苷化反应的副反应少，目标产物产率高且光学纯度高，为糖苷化反应的研究提供了一种新的设计思路。