methyl 2,3-di-O-benzyl-4,6-O-(2-naphthyl)methylene-α-D-glucopyranoside | 291314-22-2

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡喃二恶英
• 英文名称: methyl 2,3-di-O-benzyl-4,6-O-(2-naphthyl)methylene-α-D-glucopyranoside
• 英文别名: (2R,4aR,6S,7R,8S,8aR)-6-methoxy-2-naphthalen-2-yl-7,8-bis(phenylmethoxy)-4,4a,6,7,8,8a-hexahydropyrano[3,2-d][1,3]dioxine
• CAS: 291314-22-2
• 化学式: C₃₂H₃₂O₆
• 分子量: 512.602
• InChiKey: YUAUAKCSVWYENA-OXODEJSPSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.2
• 重原子数：
  38
• 可旋转键数：
  8
• 环数：
  6.0
• sp3杂化的碳原子比例：
  0.31
• 拓扑面积：
  55.4
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  methyl 2,3-di-O-benzyl-4,6-O-(2-naphthyl)methylene-α-D-glucopyranoside 在 lithium aluminium tetrahydride 、 三氯化铝 作用下， 以 乙醚 、 二氯甲烷 为溶剂， 反应 2.0h， 生成 methyl 2,3-di-O-benzyl-4-O-(2-naphthyl)methyl-α-D-glucopyranoside
  参考文献：
  名称：

  糖苷的（2-萘基）亚甲基缩醛的制备及其氢解转化为2-萘基甲基（NAP）醚†

  摘要：

  糖苷的二恶烷和二恶烷型（2-萘基）亚甲基缩醛是通过酸催化的反缩醛化反应制备的。使用AlH 3（LiAlH 4：AlCl 3 = 3：1），NaCNBH 3 -HCl或BH 3 Me 3 N-AlCl 3试剂裂解乙缩醛。4，6- O-乙缩醛与AlH 3的反应产生了4- O NAP醚，而其他两种试剂则得到了具有优异区域选择性的6- O NAP衍生物。在二氧戊环型缩醛中，所有三种试剂的裂解方向由缩醛中心的立体化学确定。赤道ø NAP /轴向羟基衍生物是从所获得的外萘基异构体; 另一方面，内萘基乙缩醛引起轴向O NAP /赤道羟基化合物的形成。NAP醚和（2-萘基）亚甲基缩醛保护基都可以通过用DDQ处理而容易地除去。

  DOI：

  10.1016/s0040-4039(00)00735-8
• 作为产物：
  描述：

  2-(dimethoxymethyl)naphthalene 在 sodium hydride 、 对甲苯磺酸 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 反应 24.0h， 生成 methyl 2,3-di-O-benzyl-4,6-O-(2-naphthyl)methylene-α-D-glucopyranoside
  参考文献：
  名称：

  Dioxane-type (2-naphthyl)methylene acetals of glycosides and their hydrogenolytic transformation into 6-O- and 4-O-(2-naphthyl)methyl (NAP) ethers

  摘要：

  alpha-, beta-D-Gluco-, galacto-, 2-deoxy-2-phthalimido-beta-D-glucopyranosides with different aglycons (methyl, allyl, p-methoxyphenyl, thioethyl) reacted with 2-naphthaldehyde dimethyl acetal to give rise to 4,6-O-(2-naphthyl)methylene acetals. The acetals were converted into fully protected compounds bearing benzoyl, benzyl, allyl, p-methoxybenzyl groups. The fully alkylated dioxane-type acetals were hydrogenolysed with AlH3 (3LiAlH(4)-AlCl3) reagent to furnish 4-O-NAP/6-OH derivatives. All acetals were treated with BH3.Me3N-AlCl3 in THF and a reverse regioselectivity was observed, producing 6-O-NAP/4-OH derivatives. Similar regioselectivity was also observed by using NaCNBH3-HCl reagent. In all reactions very mild reaction conditions were required, regioselectivity was better than 93:7, and the isolated yields were between 83-92%. All compounds were characterised by H-1 and C-13 NMR spectra. Solid-state and solution conformation of methyl 2,3-di-O-acetyl-4,6-O-(2-naphthyl)methylene-a-D-galactopyranoside were elucidated by X-ray and NMR measurements. (C) 2002 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0040-4020(02)00515-x

文献信息

• METHOD FOR PREPARING HEXOSE DERIVATIVES
  申请人：Hung Shang Cheng

  公开号：US20090105466A1

  公开（公告）日：2009-04-23

  A method for preparing hexose derivatives comprises the steps of providing a silylated hexose, treating the silylated hexose with a first carbonyl compound in the presence of a catalyst to form an ketalized hexose, treating the ketalized hexose with a second carbonyl compound followed by treating with a first reductant to form an etherized hexose, and converting the etherized hexose into a target hexose derivative, which can be 2-alcohol hexose, 3-alcohol hexose, 4-alcohol hexose, or a 6-alcohol hexose. In particular, the present invention can prepare the hexose derivatives with highly regioselective scheme to protect individual hydroxyls of monosaccharide units and install an orthogonal protecting group pattern in a one-pot manner

  制备己糖衍生物的方法包括以下步骤：提供硅烷基化的己糖，将硅烷基化的己糖与第一羰基化合物在催化剂存在下处理，形成缩酮化的己糖，将缩酮化的己糖与第二羰基化合物处理后，再用第一还原剂处理，形成醚化的己糖，并将醚化的己糖转化为目标己糖衍生物，可以是2-醇己糖、3-醇己糖、4-醇己糖或6-醇己糖。具体来说，本发明可以采用高度选择性的方案制备己糖衍生物，以保护单糖单元的各个羟基，并以一锅法安装正交保护基图案。
• Preparation of (2-naphthyl)methylene acetals of glycosides and their hydrogenolytic transformation into 2-naphthylmethyl (NAP) ethers
  作者：András Lipták、Anikó Borbás、Lóránt Jánossy、László Szilágyi

  DOI：10.1016/s0040-4039(00)00735-8

  日期：2000.6

  were prepared by acid-catalyzed transacetalization reactions. The acetals were cleaved using either AlH3 (LiAlH4:AlCl3=3:1), NaCNBH3–HCl or BH3 Me3N–AlCl3 reagents. Reaction of the 4,6-O-acetals with AlH3 yielded 4-ONAP ethers whereas the other two reagents gave 6-ONAP derivatives with excellent regioselectivity. In dioxolane-type acetals the direction of the cleavage with all three reagents is determined

  糖苷的二恶烷和二恶烷型（2-萘基）亚甲基缩醛是通过酸催化的反缩醛化反应制备的。使用AlH 3（LiAlH 4：AlCl 3 = 3：1），NaCNBH 3 -HCl或BH 3 Me 3 N-AlCl 3试剂裂解乙缩醛。4，6- O-乙缩醛与AlH 3的反应产生了4- O NAP醚，而其他两种试剂则得到了具有优异区域选择性的6- O NAP衍生物。在二氧戊环型缩醛中，所有三种试剂的裂解方向由缩醛中心的立体化学确定。赤道ø NAP /轴向羟基衍生物是从所获得的外萘基异构体; 另一方面，内萘基乙缩醛引起轴向O NAP /赤道羟基化合物的形成。NAP醚和（2-萘基）亚甲基缩醛保护基都可以通过用DDQ处理而容易地除去。
• Sequential removal of the benzyl-type protecting groups PMB and NAP by oxidative cleavage using CAN and DDQ
  作者：Joseph A Wright、Jinquan Yu、Jonathan B Spencer

  DOI：10.1016/s0040-4039(01)00563-9

  日期：2001.6

  The selective cleavage of the PMB (4-methoxybenzyl) group in the presence of the NAP (2-naphthylmethyl) group was achieved using CAN with a range of mono-saccharides. The NAP group can then be removed selectively in the presence of a benzyl group using DDQ. This provides a strategy for sequential deprotection of hydroxyl groups. (C) 2001 Elsevier Science Ltd. All rights reserved.
• Dioxane-type (2-naphthyl)methylene acetals of glycosides and their hydrogenolytic transformation into 6-O- and 4-O-(2-naphthyl)methyl (NAP) ethers
  作者：Anikó Borbás、Zoltán B Szabó、László Szilágyi、Attila Bényei、András Lipták

  DOI：10.1016/s0040-4020(02)00515-x

  日期：2002.7

  alpha-, beta-D-Gluco-, galacto-, 2-deoxy-2-phthalimido-beta-D-glucopyranosides with different aglycons (methyl, allyl, p-methoxyphenyl, thioethyl) reacted with 2-naphthaldehyde dimethyl acetal to give rise to 4,6-O-(2-naphthyl)methylene acetals. The acetals were converted into fully protected compounds bearing benzoyl, benzyl, allyl, p-methoxybenzyl groups. The fully alkylated dioxane-type acetals were hydrogenolysed with AlH3 (3LiAlH(4)-AlCl3) reagent to furnish 4-O-NAP/6-OH derivatives. All acetals were treated with BH3.Me3N-AlCl3 in THF and a reverse regioselectivity was observed, producing 6-O-NAP/4-OH derivatives. Similar regioselectivity was also observed by using NaCNBH3-HCl reagent. In all reactions very mild reaction conditions were required, regioselectivity was better than 93:7, and the isolated yields were between 83-92%. All compounds were characterised by H-1 and C-13 NMR spectra. Solid-state and solution conformation of methyl 2,3-di-O-acetyl-4,6-O-(2-naphthyl)methylene-a-D-galactopyranoside were elucidated by X-ray and NMR measurements. (C) 2002 Elsevier Science Ltd. All rights reserved.