acetic acid 2-allyl-4,5-bis-benzyloxy-6-benzyloxymethyl-tetrahydro-pyran-3-yl ester | 374900-65-9

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: acetic acid 2-allyl-4,5-bis-benzyloxy-6-benzyloxymethyl-tetrahydro-pyran-3-yl ester
• 英文别名: 3-C-(2-O-acetyl-3,4,6-tri-O-benzyl-α-D-glycopyranosyl)propene；[(2R,3S,4S,5R,6R)-4,5-bis(phenylmethoxy)-6-(phenylmethoxymethyl)-2-prop-2-enyloxan-3-yl] acetate
• CAS: 374900-65-9
• 化学式: C₃₂H₃₆O₆
• 分子量: 516.634
• InChiKey: UEPHPANXDZZLFN-OPUWLFLUSA-N

物化性质

• 沸点：
  610.8±55.0 °C(Predicted)
• 密度：
  1.16±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  5.2
• 重原子数：
  38
• 可旋转键数：
  14
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.34
• 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：

  acetic acid 2-allyl-4,5-bis-benzyloxy-6-benzyloxymethyl-tetrahydro-pyran-3-yl ester 在 sodium methylate 、 乙酸酐 、 二甲基亚砜 作用下， 以 甲醇 为溶剂， 反应 26.0h， 生成 3-C-(3,4,6-tri-O-benzyl-α-D-arabino-hex-2-ulopyranosyl)propene
  参考文献：
  名称：

  Multifunctionalized α,β-cyclopentenones from C-2 and C-4-ulopyranosyl compounds: a stereospecific rearrangement initiated by base

  摘要：

  Base treatment of O-benzyl protected C-2- or C-4-ulopyranosyl compounds (4 alpha, 4 beta, and 11) by either 10% Et3N or 1% K2CO3 in MeOH initiated a beta elimination to afford alpha,beta-unsaturated C-ulopyranosyl compounds (5 alpha, 5 beta, and 12), which further rearranged in a stereocontrolled manner to multifuctionalized alpha,beta-cyclopentenones (6 and 14) in 70-80% yield. Both C-alpha- and C-beta-2-ulosides (5 alpha and 5 beta) produced the same cyclopentenone 6, indicating that a 1,2-enolate is formed prior to the cleavage of the C-5-O bond. Because 6 is racemic, it was probably formed by the intramolecular cycloaldolization of two equally populated enantiomeric intermediates. When treated with 90% Et3N in MeOH, 5 alpha yielded almost exclusively 15 (isomer of 6), which was formed by a migration of the double bond in 5 alpha during the previously described rearrangement. Thus either 6 or 15 was the major product, depending on the base used. (C) 2001 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0008-6215(01)00187-2
• 作为产物：
  描述：

  乙酸酐 、 3-(3,4,6-tri-O-benzyl-α-D-glucopyranosyl)-1-propene 在 吡啶 作用下， 生成 acetic acid 2-allyl-4,5-bis-benzyloxy-6-benzyloxymethyl-tetrahydro-pyran-3-yl ester
  参考文献：
  名称：

  Exploiting the cross-metathesis reaction in the synthesis of pseudo-oligosaccharides

  摘要：

  本文提出了一种基于不同糖烯之间的交叉易位反应，随后通过所得异二聚体的分子内环化来合成伪寡糖的方法。特别是，针对多种糖烯底物，探究并比较了两种替代方法的相对效率：直接的交叉易位反应和两步程序（自我易位后进行交叉易位）。此外，还报告了一些使用碘作为亲电促进剂的分子内环化的代表性实例。

  DOI：

  10.1039/b822989a

文献信息

• Synthesis of oxa-aza spirobicycles by intramolecular hydrogen atom transfer promoted by N-radicals in carbohydrate systems
  作者：Angeles Martín、Inés Pérez-Martín、Ernesto Suárez

  DOI：10.1016/j.tet.2009.05.049

  日期：2009.8

  The nitrogen-centred radical generated by reaction of an N-phosphoramidate or N-cyanamide, attached to a tri- or tetramethylene tether extended from the C-1 of a carbohydrate, with (diacetoxyiodo)benzene (DIB) and iodine can undergo a regio- and stereoselective intramolecular hydrogen atom transfer (HAT) reaction to furnish four different oxa-azaspirobicyclic systems: 1-oxa-6-azaspiro[4.4]nonane, 1-oxa-6-azaspiro[4

  通过的反应所产生的氮中心基团Ñ -phosphoramidate或N-氨腈，连接到三-或四亚甲基系绳从C-1碳水化合物，与（二乙酰氧基碘）苯（DIB）扩展和碘可经历区域选择性-和立体选择性分子内氢原子转移（HAT）反应以提供四个不同的oxa-azaspiro双环系统：1-oxa-6-azaspiro [4.4]壬烷，1-oxa-6-azaspiro [4.5]癸烷，6-oxa-1- azaspiro [4.5]癸烷和1-oxa-7-azaspiro [5.5]十一烷。提出了串联的1，5-或1，6-HAT-氧化-亲核环化机理。
• Epimerization of 2‘-Carbonylalkyl-<i>C</i>-Glycosides via Enolation, β-Elimination and Intramolecular Cycloaddition
  作者：Zerong Wang、Huawu Shao、Edith Lacroix、Shih-Hsiung Wu、Harold J. Jennings、Wei Zou

  DOI：10.1021/jo034446k

  日期：2003.10.1

  as an intermediate. When 2'-aldehyde (36) and 2'-ketone (41) of 2,3-di-O-benzyl-alpha/beta-l-C-arabinofuranoside were used as substrates we were able to obtain the respective equatorial alpha-C-arabinopyranosides (37 and 42). These observations confirmed that the epimerization involves an acyclic alpha,beta-unsaturated aldehyde or ketone, which is formed by the enolation of 2'-carbonyl-alpha-C-glycoside

  用4％NaOMe处理葡萄糖，半乳糖，甘露糖，2-脱氧和2-叠氮基糖的2'-羰基-α-C-糖吡喃糖苷导致端基异构体异构化，使其各自的β-端基异构体具有良好或优异的收率。α-C-吡喃半乳糖苷（10）的2'-醛在氘代甲醇中的差向异构化作用使β-端基异构体在1'-位具有唯一的氘代取代作用，排除了外糖参与的可能性中间体。当使用2,3-二-O-苄基-α/β-1C-阿拉伯呋喃糖苷的2'-醛（36）和2'-酮（41）作为底物时，我们能够获得各自的赤道α-C-阿拉伯吡喃糖苷（37和42）。这些观察结果证实，差向异构体涉及无环的α，β-不饱和醛或酮，它是由2'-羰基-α-C-糖苷的烯醇化和随后的β-消除形成的。此后发生分子内杂-迈克尔环加成反应，导致形成热力学控制的稳定产物，该产物仅是赤道的C-糖吡喃糖苷，但2'-羰基-C-呋喃糖苷除外，其中获得了两种端基异构体的混合物。
• Novel Zinc (II)-Mediated Epimerization of 2‘-Carbonylalkyl-α-<i>C</i>-glycopyranosides to Their β-Anomers
  作者：Huawu Shao、Zerong Wang、Edith Lacroix、Shih-Hsiung Wu、Harold J. Jennings、Wei Zou

  DOI：10.1021/ja017430p

  日期：2002.3.1

  presence of zinc acetate. The β-stereoselectivity is independent of the neighboring group at 2-O-substitution of sugar substrates. Therefore, this provides a particularly useful method for the preparation of manno-β-C-glycosides. The epimerization is likely initiated by the formation of Zn-enolate that is stabilized by intramolecular chelation to the pyranose ring-oxygen to form a syn chair-boat structure

  α-C-糖苷的 2'-醛和 2'-酮，包括葡糖、半乳糖和甘露糖系列，在碱性条件下和在醋酸锌的存在。β-立体选择性与糖底物 2-O-取代的相邻基团无关。因此，这为制备甘露糖-β-C-糖苷提供了一种特别有用的方法。差向异构化可能是由 Zn-烯醇化物的形成引发的，Zn-烯醇化物通过与吡喃糖环-氧的分子内螯合而稳定以形成合成椅船结构。由于 Zn-O 配位产生的活化，C1-O 键发生裂变，导致吡喃糖环打开，随后自发地发生构象变化。
• Stereoselective synthesis of dioxabicycles from 1-<i>C</i>-allyl-2-<i>O</i>-benzyl-glycosides — An intramolecular cyclization between 2-<i>O</i>-benzyl oxygen and the allyl double bond
  作者：An-Tai Wu、Tian Yi、Huawu Shao、Shih-Hsiung Wu、Wei Zou

  DOI：10.1139/v06-046

  日期：2006.4.1

  Addition of a proton to the double bond of 1-C-allyl-O-benzylglycosides gave a 2′-carbonium ion, which in turn reacted intramolecularly, in a regio- and diastereo-selective manner, with the nucleophilic oxygen of the 2-O-benzyl group to form an oxonium intermediate. Subsequent cleavage of the benzyl C—O bond led to dioxabicycles in moderate yields. Surprisingly, opposite diastereoselectivities were observed from 1-C-allylglycofuranosides and 1-C-allylglycopyranosides, which produced 2,2′-trans- and 2,2′-cis-dioxabicycles, respectively.Key words: C-glycoside, olefin, cyclization, oxocarbonium, dioxabicycles.

  在 1-C-烯丙基-O-苄基糖苷的双键上加入一个质子会产生一个 2′-羰基离子，该离子又会以区域和非对映选择性的方式与 2-O-苄基的亲核氧发生分子内反应，形成一个羰基中间体。随后，苄基 CO 键裂解产生二恶英双环，产量适中。令人惊讶的是，1-C-烯丙基甘呋喃糖苷和 1-C-烯丙基甘吡喃糖苷的非对映选择性相反，它们分别生成 2,2′- 反式和 2,2′- 顺式二氧杂环：C-糖苷 烯烃 环化 氧化羰 二氧杂环
• 1,2-Migration of 2‘-Oxoalkyl Group and Concomitant Synthesis of 2-<i>C</i>-Branched <i>O</i>-, <i>S</i>-Glycosides and Glycosyl Azides via 1,2-Cyclopropanated Sugars
  作者：Huawu Shao、Sanchai Ekthawatchai、Chien-Sheng Chen、Shih-Hsiung Wu、Wei Zou

  DOI：10.1021/jo0502854

  日期：2005.6.1

  Treatment of 2'-oxoalkyl 2-O-Ms(Ts)-alpha-C-mannosides (4, 5, and 6) with base resulted in 1,2-cyclopropanation via an intramolecular S(N)2 reaction due to their 1,2-trans-diaxial configurations. The 1,2-cyclopropanated sugars (10 and 13) were reacted with various alcohols, thiols, and sodium azide to produce 2-C-branched O- and S-glycosides and glycosyl azides (11, 14-28) in good to excellent yields. In contrast, 1,2-cis 2'-oxoalkyl 2-O-Ms(Ts)-alpha-C-glucoside 9 formed an acyclic conjugated aldehyde (31) under basic conditions, which occurred by 1'-enolation followed by beta-elimination. An intramolecular Michael addition from 31 produced 2-O-Ms-beta-C-glucoside 30 as a major product. However, due to the electron-withdrawing effect exerted by 2-O-Ms compound 31 also undergoes a C2 epimerization to form 32. Thereafter, the intramolecular Michael addition led to the formation of both 1,2-trans 2'-oxoalkyl 2-O-Ms-alpha-C-mannoside 4 and its beta-anomer (33). Because beta-elimination/Michael addition and C2 epimerization are reversible reactions, equilibriums among 9, 31, 30, 32, 33, and 4 were established, which included the transformation of 1,2-cis C-glucoside 9 into 1,2-trans C-mannoside 4. The subsequent 1,2-cyclopropanation of 4 was an irreversible reaction yielding 1,2-cyclopropanated 10 and further conversion to 1,2-migration products (11 and 12).