1-O-benzyl-3,4-O-isopropylidene-D-erythritol (12) and 2-O-benzyl-3,4-O-isopropylidene-D-erythritol | 111462-38-5

• 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-O-benzyl-3,4-O-isopropylidene-D-erythritol (12) and 2-O-benzyl-3,4-O-isopropylidene-D-erythritol
• 英文别名: (2S)-2-(benzyloxy)-2-[(2'R)-2',2'-dimethyl-1',3'-dioxolan-4'-yl]ethanol；(1S,4'R)-1-benzyloxy-1-(2,2-dimethyl-1,3-dioxolane-4-yl)ethan-2-ol；(S)-2-(benzyloxy)-2-((R)-2,2-dimethyl-1,3-dioxolan-4-yl)ethanol；(S)-2-(benzyloxy)-2-[(S)-2,2-dimethyl-1,3-dioxolan-4-yl]ethanol；2-O-benzyl-3,4-O-isopropylidene-D-erythritol；2-O-benzyl-3,4-O-isopropylidene-D-erytritol；(2S,3S)-2-Benzyloxy-3,4-O-isopropylidene-butan-1-OL；(2S)-2-[(4R)-2,2-dimethyl-1,3-dioxolan-4-yl]-2-phenylmethoxyethanol
• CAS: 111462-38-5
• 化学式: C₁₄H₂₀O₄
• 分子量: 252.31
• InChiKey: BCACQGHYULTSHT-QWHCGFSZSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.2
• 重原子数：
  18
• 可旋转键数：
  5
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.57
• 拓扑面积：
  47.9
• 氢给体数：
  1
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  1-O-benzyl-3,4-O-isopropylidene-D-erythritol (12) and 2-O-benzyl-3,4-O-isopropylidene-D-erythritol 在 Lindlar's catalyst 、 四氧化锇 草酰氯 、 1,2-diphenyl-N,N'-bis[(2,4,6-trimethylphenyl)methyl]-1,2-diaminoethane 、 氢气 、 sodium hydride 、 二甲基亚砜 、 三乙胺 作用下， 以 四氢呋喃 、 甲醇 、 二氯甲烷 为溶剂， 反应 20.0h， 生成 (3S,4S,5R)-4,5-Bis-benzyloxy-1-((2S,3R,5R,6S)-5-benzyloxy-2-benzyloxymethyl-6-methoxy-tetrahydro-pyran-3-yl)-5-((R)-2,2-dimethyl-[1,3]dioxolan-4-yl)-3-(4-methoxy-benzyloxy)-pentan-2-one
  参考文献：
  名称：

  Preferred conformation of C-glycosides. 8. Synthesis of 1,4-linked carbon disaccharides

  摘要：

  DOI：

  10.1021/jo00028a017
• 作为产物：
  描述：

  methyl 3,4:5,6-di-O-isopropylidene-D-gluconate 在 palladium on activated charcoal 咪唑 、 四氯化碳 、 氢气 、 sodium acetate 、 臭氧 、 三苯基膦 、 sodium t-butanolate 作用下， 以 甲醇 、 二氯甲烷 、 N,N-二甲基甲酰胺 为溶剂， -78.0~30.0 ℃ 、344.74 kPa 条件下， 反应 21.67h， 生成 1-O-benzyl-3,4-O-isopropylidene-D-erythritol (12) and 2-O-benzyl-3,4-O-isopropylidene-D-erythritol
  参考文献：
  名称：

  Convenient Enantiopure Synthesis of (2S,3R)-2-O-Benzyl-3,4-O-isopropylidene-d-erythritol from d-(+)-Glucono-δ-lactone: A Potential C₄ Chiral Building Block

  摘要：

  一种新型便捷的合成(2S,3R)-2-O-苄基-3,4-O-异丙烯基- d-赤藓糖醇的方法已经实现，起始原料为极其廉价且商业上可获得的 d-(+)-葡萄糖-δ-内酯。该方法涉及两次通过臭氧解聚的碳原子切除。内在的立体化学确保了目标化合物的对映体纯度。

  DOI：

  10.1055/s-2005-869986

文献信息

• Total synthesis and the anticancer activity of (+)-spisulosine
  作者：Milica Fabišíková、Miroslava Martinková、Simona Hirková、Jozef Gonda、Martina Bago Pilátová、Gabriela Gönciová

  DOI：10.1016/j.carres.2016.09.010

  日期：2016.11

  The total synthesis of the anticancer agent (+)-spisulosine has been accomplished. The strategy involved a substrate-controlled aza-Claisen rearrangement to establish the erythro-configured amino-alcohol motif followed by deoxygenation to create a methyl side-chain. Subsequent Wittig olefination then permitted the construction of the carbon backbone of the target molecule. To investigate the antiproliferative

  已经完成了抗癌药（+）-spisulosine的全合成。该策略涉及底物控制的aza-Claisen重排以建立赤型构型的氨基醇基序，然后进行脱氧以创建甲基侧链。随后随后的维蒂希烯化反应允许构建靶分子的碳主链。为研究1的抗增殖作用，在一组6种人类恶性细胞系上检查了其生物学特性，并证明了1对至少5种评估系具有显着的抗癌活性，IC50 <1μM（MCF-7，HTC- 116，Caco-2，Jurkat和HeLa）。
• A Defunctionalization Concept for the Convenient Synthesis of Bis(5-arylfuran-2-yl)methane Scaffolds
  作者：Praveen Kumar Tiwari、Tufan Mukhopadhyay、Indrapal Singh Aidhen

  DOI：10.1002/ejoc.201301319

  日期：2013.12

  The bis(5-arylfuran-2-yl)methane framework has been obtained through defunctionalization of aryl ketones, derived from abundantly available L-(+)-tartaric acid, under the influence of acid. The stereocomponents present in these starting aryl ketones have been found to be insignificant for this transformation.

  双(5-芳基呋喃-2-基)甲烷骨架是通过芳基酮的去官能化获得的，芳基酮衍生自大量可用的L-(+)-酒石酸，在酸的影响下。已经发现这些起始芳基酮中存在的立体组分对于这种转化是微不足道的。
• Stereoselective allylation for preparation of L-hexose derivatives
  作者：D.R. Williams、Franz D. Klingler

  DOI：10.1016/s0040-4039(01)81010-8

  日期：1987.1

  The reaction of allyltrimethylsilane with α,β-dialkoxyaldehydes is catalyzed by magnesium bromide, and provides for a highly stereoselective allylation which is predicted by α-chelation of the Lewis acid. The observed stereocontrol is opposite to that generally obtained from a variety of common allylation reagents.

  烯丙基三甲基硅烷与α，β-二烷氧基醛的反应被溴化镁催化，并提供了高度立体选择性的烯丙基化，其通过路易斯酸的α-螯合来预测。观察到的立体控制与通常从多种常见的烯丙基化试剂获得的立体控制相反。
• Synthesis and Glycosidase Inhibitory Activities of Pyrrolidines and Piperidines withN-(Polyhydroxyalkyl) Side Chains
  作者：Sabrina Boutefnouchet、István Moldvai、Eszter Gács-Baitz、Claudia Bello、Pierre Vogel

  DOI：10.1002/ejoc.200700027

  日期：2007.6

  Amidification of L-proline (3) with (+)-(R,R)-6 and (–)-(S,S)-tartaric anhydride diacetate (7) gave N-substituted L-proline derivatives 8a,b, respectively. Acids 8a,b were transformed into diesters 9a,b with MeOH/HCl. Similar reactions with methyl (2S,4R)-4 and (2R,4S)-4-acetoxypipecolate (5) led to bicyclic lactams 14a,b and 15a. Compounds 8a,b were converted into N-(trihydroxybutyl)pyrrolidine derivatives

  L-脯氨酸 (3) 与 (+)-(R,R)-6 和 (-)-(S,S)-酒石酸酐二乙酸酯 (7) 的酰胺化分别得到 N-取代的 L-脯氨酸衍生物 8a,b . 用MeOH/HCl将酸8a、b转化为二酯9a、b。与 (2S,4R)-4 和 (2R,4S)-4-乙酰氧基哌可酸甲酯 (5) 的类似反应生成双环内酰胺 14a、b 和 15a。化合物8a、b被转化为N-(三羟基丁基)吡咯烷衍生物8c、d、10a、b和11a、b。(2S,4R)-20a 和 (2R,4S)-4-乙酰氧基-N-[(2S,3S)-1,2,3-三羟基丁基]哌可酸甲酯 (20b) 通过置换 (-)-( 2S,2S)-2-O-benzyl-3,4-O-isopropylidene-1-deoxy-1-iodthreitol (19) 通过 4 和 5。化合物 20a,b 被转化为 (2S,4R,2'S, 2'S)-21a 和 (2R
• Enantioselective Synthesis of Ethyl 4,5,7,8,9-Penta-O-acetyl-2,6-anhydro- 3-deoxy-D-erythro-L-gluca-nononate: a 2-Monodeoxygenated Derivative of `2-Keto-3-deoxy-D-glycero-D-galacto-nononic Acid'
  作者：Xin Shen、Yu-Lin Wu、Yikang Wu

  DOI：10.1002/(sici)1522-2675(20000510)83:5<943::aid-hlca943>3.0.co;2-h

  日期：2000.5.10

  A study aimed at developing an enantioselective synthesis of the title compound 23, a 2-monodeoxy analogue of;he naturally occurring (+)-2-keto-3-deoxy-D-glycero-D-galacto-2-nononic acid (KDN),is reported. From D-mannose as starting material, the chiral 1,3-diene 10, activated by a silyloxy substituent at C(2), was prepared in six steps (Scheme I). However, the intermediates were often contaminated with varying amounts of by-products arising from overoxidation during cleavage with periodic acid. An alternative route starting from the inexpensive and readily available D-isoascorbic acid (12), though a little longer than the first, satisfactorily circumvented the purification problem and led to the desired dienes 17 in good yields (scheme2). The [Co-II(S.S)-(+)-salen]-catalyzed hetero-Diels-Alder reactions of the aforementioned dienes with ethyl glyoxylate proceeded smoothly at room temperature, giving the dihydropyrano adducts 18 in moderate yields (Scheme 3). Dihydroxylation of 18a followed by reduction of the keto function gave the desired 4,5-trans dihydroxy moiety of the KDN framework (Scheme 4, see 21). The spectroscopic data of the penta-O-acetylated 2-deoxy-KDN ethyl ester 23 were consistent with those reported for the corresponding methyl ester derived from natural KDN.