3-(3,4,6-tri-O-benzyl-β-D-glucopyranosyl)-1-propene | 161275-25-8

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 3-(3,4,6-tri-O-benzyl-β-D-glucopyranosyl)-1-propene
• 英文别名: C-allyl 3,4,6-tri-O-benzyl-β-D-glucopyranoside；3-C-(3,4,6-tri-O-benzyl-β-D-glycopyranosyl)propene；(2S,3S,4R,5R,6R)-4,5-bis(benzyloxy)-6-[(benzyloxy)methyl]-2-(prop-2-en-1-yl)oxan-3-ol；3-C-(3,4,6-tri-O-benzyl-β-D-glucopyranosyl)1-propene；(2S,3S,4R,5R,6R)-4,5-bis(phenylmethoxy)-6-(phenylmethoxymethyl)-2-prop-2-enyloxan-3-ol
• CAS: 161275-25-8
• 化学式: C₃₀H₃₄O₅
• 分子量: 474.597
• InChiKey: UYWKXHISDGPRTR-PGVCKJCBSA-N

物化性质

• 熔点：
  69-71 °C
• 沸点：
  607.9±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)：
  4.6
• 重原子数：
  35
• 可旋转键数：
  12
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.33
• 拓扑面积：
  57.2
• 氢给体数：
  1
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  3-(3,4,6-tri-O-benzyl-β-D-glucopyranosyl)-1-propene 在 间氯过氧苯甲酸 作用下， 以 二氯甲烷 为溶剂， 反应 240.0h， 以70%的产率得到
  参考文献：
  名称：

  An efficient stereoselective synthesis of enantiomerically pure aziridine derivatives of allyl β-d-glucopyranosides asymmetrically induced by a glucide moiety

  摘要：

  The enantiomerically pure title aziridines were obtained by regioselective azidolysis of the 2',3'-epoxy derivatives of allyl 3,4,6-tri-O-benzyl-beta-D-glucopyranosides, followed by cyclization of the corresponding azido alcohols by means of the PPh3 protocol. Enantiomerically pure starting epoxides were prepared by epoxidation of the corresponding allyl 3,4,6-tri-O-benzyl-beta-D-glucopyranosides asymmetrically induced by a glucide moiety. (C) 1998 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0957-4166(98)00427-3
• 作为产物：
  描述：

  3-C-(2-O-acetyl-3,4,6-tri-O-benzyl-β-D-glycopyranosyl)propene 在 sodium methylate 作用下， 以 甲醇 为溶剂， 反应 2.0h， 以91%的产率得到3-(3,4,6-tri-O-benzyl-β-D-glucopyranosyl)-1-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

文献信息

• 1,5-Hydrogen Atom Transfer/Surzur–Tanner Rearrangement: A Radical Cascade Approach for the Synthesis of 1,6-Dioxaspiro[4.5]decane and 6,8-Dioxabicyclo[3.2.1]octane Scaffolds in Carbohydrate Systems
  作者：Elisa I. León、Ángeles Martín、Adrián S. Montes、Inés Pérez-Martín、María del Sol Rodríguez、Ernesto Suárez

  DOI：10.1021/acs.joc.1c01376

  日期：2021.11.5

  alkoxyl radicals were generated by the reaction of the corresponding N-alkoxyphthalimides with group 14 hydrides [n-Bu3SnH(D) and (TMS)3SiH], and in comparative terms, the reaction was also initiated by visible light photocatalysis using the Hantzsch ester/fac-Ir(ppy)3 procedure. Special attention was devoted to the influence of the relative stereochemistry of the centers involved in the radical sequence

  已经在一系列具有 3 -C- ( α, β- d , l - 吡喃葡萄糖基）1-丙醇和C -（α- d , l -吡喃葡萄糖基）甲醇结构，由手性池d - 和l - 糖制备。使用乙酰氧基和二苯氧基磷酸酯氧基作为离去基团可有效构建 10-deoxy-1,6-dioxaspiro[4.5]decane 和 4-deoxy-6,8-dioxabicyclo[3.2.1]octane 骨架。烷氧基自由基由相应的N反应生成-烷氧基邻苯二甲酰亚胺与第 14 族氢化物 [ n -Bu 3 SnH(D) 和 (TMS) 3 SiH]，比较而言，该反应也由使用 Hantzsch 酯/ fac -Ir(ppy) 3程序的可见光光催化引发. 特别关注自由基序列中涉及的中心的相对立体化学对反应结果的影响。将BF 3 •Et 2 O 作为催化剂添加到自由基序列中导致所需双环缩酮的产率显着增加。
• A Short Sequence for the Iterative Synthesis of Fused Polyethers
  作者：Frédéric Elustondo、Venkaiah Chintalapudi、J. Stephen Clark

  DOI：10.1002/hlca.201900161

  日期：2019.9

  A simple and efficient four‐step sequence for the synthesis of fused polyether arrays has been developed. Cyclic ethers are installed by sequential alkynyl ether formation, carbocupration, ring‐closing metathesis and hydroboration with acidic workup. Crucially, the alkene required for the subsequent ring formation by ring‐closing metathesis is present in the substrate but is masked in the form of a

  已经开发了一种简单有效的四步法合成融合聚醚阵列。通过依次进行炔基醚的形成，碳键化，闭环复分解和在酸性条件下进行的硼氢化反应来安装环醚。至关重要的是，通过闭环复分解形成后续环所需的烯烃存在于基底中，但以乙烯基硅烷的形式被掩盖，从而阻止了侧链的竞争复分解。通过硼氢化反应和随后的酸介导的彼得森消除中间羟基硅烷，可从非反应性乙烯基硅烷生成反应性烯烃。
• Zinc-Mediated Synthesis of α-<i>C</i>-Glycosides from 1,2-Anhydroglycosides
  作者：Song Xue、Kai-Zhen Han、Lin He、Qing-Xiang Guo

  DOI：10.1055/s-2003-38751

  日期：——

  α-C-Glycosides have been prepared by the addition of organozinc reagents to glycal epoxides. Dialkyl and diaryl zinc reagents in the presence of CF3COOH provide the corresponding α-glycosides in 53-82% yields. Organozinc chlorides RZnCl formed by the reaction RLi with zinc chloride can also be successfully applied to this coupling reaction with high α-selectivity.

  α-C-糖苷是通过将有机锌试剂加入糖醇环氧化物制备的。在CF3COOH的存在下，二烷基和二芳基锌试剂能以53-82%的产率提供相应的α-糖苷。由RLi与氯化锌反应形成的有机锌氯化物RZnCl也可以成功应用于这种偶联反应，并具有很高的α-选择性。
• The Synthesis of Some Epoxyalkyl b-C-Glycosides as Potential Inhibitors of b-Glucan Hydrolases
  作者：Wayne M. Best、Vito Ferro、Julia Harle、Robert V. Stick、D. Matthew G. Tilbrook

  DOI：10.1071/c97015

  日期：——

  The treatment of tetra-O-benzyl-D-glucono-1,5-lactone with various alkenylmagnesium halides gave the intermediate lactols which, upon reduction (Et3SiH/BF3) and protecting group manipulation, yielded alkenyl tetra-O-acetyl-β-D-C-glucopyranosides in good yield. These β-D-C-glucosides were precursors of the epoxyalkyl β-D-C-glucopyranosides, themselves putative inhibitors of b-glucan hydrolases. Similar additions of Grignard reagents to per-benzylated cellobionolactone were not as successful in yielding epoxyalkyl β-C-cellobiosides. The addition of Grignard reagents to 1,2-anhydro-3,4,6-tri-O-benzyl-α-D- glucose offers a viable alternative route to the prop-2-enyl β-D-C-glucoside, but not to the but-3-enyl and pent-4-enyl counterparts. Likewise, the addition of Grignard reagents to a 1,2-anhydro cellobiose gave disappointing results. Preliminary results are reported for a novel approach to alkenyl β-D-C-glucosides by the alkylation of nitromethyl β-D-C-glucosides.

  用各种烯基卤化镁处理四-O-苄基-D-葡萄糖醛酸-1,5-内酯，可以得到中间内酯。 与各种烯基卤化镁处理后得到中间体内酯、 经还原（Et3SiH/BF3） 和保护基操作后，得到烯基 四-O-乙酰基-β-D-C-吡喃葡萄糖苷 产量很高。这些β-D-C-吡喃葡萄糖苷是 环氧烷基 β-D-C-吡喃葡萄糖苷的前体、 这些β-D-C-吡喃葡萄糖苷是环氧烷基β-D-C-吡喃葡萄糖苷的前体。类似的 格氏试剂的效果并不理想。 生成环氧烷基 β-C-纤维二糖苷。在 格氏试剂添加到 1,2-脱水-3,4,6-三-O-苄基-α-D-葡萄糖提供了 丙-2-烯基-β-D-葡萄糖的一种可行的替代途径。 β-D-C-葡萄糖苷提供了可行的替代途径，但并没有提供丁-3-烯基和 戊-4-烯基的对应物。同样，将格氏试剂加入到 1,2-anhydro cellobiose 的结果令人失望。初步结果 报告了烯基 β-D-C-葡萄糖苷的新方法的初步结果。 β-D-C-葡萄糖苷的新方法的初步结果。
• Preparation and Transmetallation of a Triphenylstannyl ?-D-Glucopyranoside: A highly stereoselective route to ?-D-C-glycosidesvia glycosyl dianions
  作者：Oliver Frey、Matthias Hoffmann、Valentin Wittmann、Horst Kessler、Peter Uhlmann、Andrea Vasella

  DOI：10.1002/hlca.19940770730

  日期：1994.11.2

  The triphenylstannyl β-D-glucopyranoside 4 was synthesized in one step from the 1,2-anhydro-α-D-glucopyranose 3 with (triphenylstannyl)lithium (Scheme 1). Transmetallation of 4 with excess BuLi, followed by quenching the dianion 7 with CD3OD gave (1S)-1,5-anhydro-3,4,6-tri-O-benzyl-[1-2H]-D- glucitol (8) in 81% yield (Scheme 2). Trapping of 7 with benzaldehyde, isobutyraldehyde, or acroleine gave the

  由1,2-脱水-α-D-吡喃葡萄糖3与（三苯基锡烷基）锂一步合成三苯基锡烷基β-D-吡喃葡萄糖苷4（方案1）。的金属转移4用过量的丁基锂，随后淬火二价阴离子7与CD 3 OD，得到（1个小号）-1,5-脱水-3,4,6-三ö苄基- [1- 2 H] -D-葡萄糖醇（8），产率为81％（方案2）。用苯甲醛，异丁醛或丙烯醛诱捕7得到预期的β-D构型的产物11、12和13丰产。由酰基氯例如乙酰基或苯甲酰氯制备C-酰基糖苷是不可行的，但是将苯甲腈添加到7中产生84％的苯甲酰化产物14。用MeI处理7导致15（30％）以及18的40％，C-烷基化伴随卤素-金属交换。预先加入锂2- thienylcyanocuprate的的产率增加15％至50％，并使用硫酸二甲酯代替将MeI导致77％15。除了使用烯丙基溴作为亲电试剂以外，没有检测到α-D-异头物，它以1：1的异构体混合物形式生成16和17。