methyl 6-amino-2,3,4-tri-O-benzyl-6-deoxy-α-D-mannopyranoside | 674302-89-7

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: methyl 6-amino-2,3,4-tri-O-benzyl-6-deoxy-α-D-mannopyranoside
• 英文别名: [(2R,3R,4S,5S,6S)-6-methoxy-3,4,5-tris(phenylmethoxy)oxan-2-yl]methanamine
• CAS: 674302-89-7
• 化学式: C₂₈H₃₃NO₅
• 分子量: 463.574
• InChiKey: IGIHLLRSHTZZPN-MASCHLQQSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.2
• 重原子数：
  34
• 可旋转键数：
  11
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.36
• 拓扑面积：
  72.2
• 氢给体数：
  1
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  methyl 6-amino-2,3,4-tri-O-benzyl-6-deoxy-α-D-mannopyranoside 在 乙酸酐 、 三乙胺 、 三氯氧磷 作用下， 以 甲醇 、 二氯甲烷 、 水 为溶剂， 反应 29.5h， 生成
  参考文献：
  名称：

  A focused sulfated glycoconjugate Ugi library for probing heparan sulfate-binding angiogenic growth factors

  摘要：

  A library of small molecule heparan sulfate (HS) mimetics was synthesized by employing the Ugi four-component condensation of D-mannopyranoside-derived isocyanides with formaldehyde as the carbonyl component and a selection of carboxylic acids and amines, followed by sulfonation. The library was used to probe the subtle differences surrounding the ionic binding sites of three HS-binding angiogenic growth factors (FGF-1, FGF-2 and VEGF). Each compound features 3 or 4 sulfo groups which serve to anchor the ligand to the HS-binding site of the protein, with a diverse array of functionality in place extending from C-1 or C-6 to probe for adjacent favorable binding interactions. Selectivity of binding to these proteins was clearly observed and supported by molecular docking calculations. (C) 2012 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.bmcl.2012.08.001
• 作为产物：
  描述：

  methyl 6-O-acetyl-2,3,4-tri-O-benzyl-α-D-mannopyranoside 在 偶氮二甲酸二异丙酯 、 sodium methylate 、 三苯基膦 、 肼 作用下， 以 四氢呋喃 、 甲醇 、 乙醇 为溶剂， 反应 1.0h， 生成 methyl 6-amino-2,3,4-tri-O-benzyl-6-deoxy-α-D-mannopyranoside
  参考文献：
  名称：

  不对称脲基连接二糖的高效合成

  摘要：

  有效地合成了五种非对称的脲连接二糖，其中两个吡喃糖苷单元结合在 1⇄2、1⇄4 和 1⇄6 位置。采用温和且安全的程序，其中糖基异氰酸酯与糖基胺偶联。(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004)

  DOI：

  10.1002/ejoc.200300483

文献信息

• Iridium-catalysed condensation of alcohols and amines as a method for aminosugar synthesis
  作者：Ian Cumpstey、Santosh Agrawal、K. Eszter Borbas、Belén Martín-Matute

  DOI：10.1039/c1cc12800k

  日期：——

  Primary carbohydrate amines at primary and secondary carbons are alkylated by alcohols in the presence of [Cp*IrCl2]2. When primary carbohydrate alcohols are used as the coupling partners and in the presence of Cs2CO3, amine-linked pseudodisaccharides are obtained. Secondary carbohydrate alcohols are unaffected under these conditions, which allows regioselective reactions.

  在[Cp*IrCl2]2的存在下，初级和次级的碳水化合物氨基会被醇所烷基化。当使用初级碳水化合物醇作为耦合伴侣并在Cs2CO3的存在下，可以得到氨基连接的拟二糖。在这些条件下，次级碳水化合物醇不会受到影响，从而实现了区域选择性反应。
• Investigations into the synthesis of amine-linked neodisaccharides
  作者：Tashfeen Akhtar、Ian Cumpstey

  DOI：10.1016/j.tetlet.2007.10.039

  日期：2007.12

  glucose-6-sulfonamides as nucleophiles and primary carbohydrate alcohols as electrophiles. Primary–secondary linked compounds were synthesised by epoxide ring opening with carbohydrate 6-amines. Deprotection of all neodisaccharides was carried out using dissolving metal reduction.

  六个尾到尾胺连接的新二糖被合成为潜在的糖模拟物。初级-初级连接的化合物是使用Mitsunobu化学方法合成的，其中葡萄糖-6-磺酰胺为亲核试剂，初级糖醇为亲电试剂。伯-仲连接的化合物是通过与碳水化合物6-胺的环氧开环合成的。使用溶解性金属还原进行所有新二糖的脱保护。
• Amine-linked diglycosides: Synthesis facilitated by the enhanced reactivity of allylic electrophiles, and glycosidase inhibition assays
  作者：Ian Cumpstey、Jens Frigell、Elias Pershagen、Tashfeen Akhtar、Elena Moreno-Clavijo、Inmaculada Robina、Dominic S Alonzi、Terry D Butters

  DOI：10.3762/bjoc.7.128

  日期：——

  Diglycose derivatives, consisting of two monosaccharides linked at non-anomeric positions by a bridging nitrogen atom, have been synthesised. Conversion of one of the precursor monosaccharide coupling components into an unsaturated derivative enhances its electrophilicity at the allylic position, facilitating coupling reactions. Mitsunobu coupling between nosylamides and 2,3-unsaturated-4-alcohols gave the 4-amino-pseudodisaccharides with inversion of configuration as single regio- and diastereoisomers. A palladium-catalysed coupling between an amine and a 2,3-unsaturated 4-trichloroacetimidate gave a 2-amino-pseudodisaccharide as the major product, along with other minor products. Derivatisation of the C=C double bond in pseudodisaccharides allowed the formation of Man(N4–6)Glc and Man(N4–6)Man diglycosides. The amine-linked diglycosides were found to show weak glycosidase inhibitory activity.

  由两个单糖通过桥接氮原子在非异头位置连接而成的双糖衍生物已经合成出来。将其中一个前体单糖耦合组分转化为不饱和衍生物，增强了其在烯丙基位置的亲电性，从而促进了耦合反应。nosyl酰胺和2,3-不饱和-4-醇之间的Mitsunobu耦合得到了反转构型的4-氨基-假双糖，作为单一的区位和对映异构体。胺和2,3-不饱和的4-三氯乙酰亚胺之间的钯催化耦合得到了2-氨基-假双糖作为主要产物，同时还得到了其他次要产物。在假双糖中对C=C双键的衍生化允许形成Man(N4–6)Glc和Man(N4–6)Man双糖苷。发现胺连接的双糖苷显示出较弱的糖苷酶抑制活性。
• Palladium(II)-Catalyzed Rearrangement of Glycal Trichloroacetimidates: Application to the Stereoselective Synthesis of Glycosyl Ureas
  作者：Gregory J. Mercer、Jaemoon Yang、Matthew J. McKay、Hien M. Nguyen

  DOI：10.1021/ja803378k

  日期：2008.8.1

  O- and N-glycosidic bonds are replaced with the urea-glycosidic linkages, has recently emerged with applications in the field of aminoglycoside antibiotics. We have developed a novel method for the stereoselective synthesis of alpha- and beta-glycosyl ureas via Pd(II)-catalyzed rearrangement of glycal trichloroacetimidates. In our approach, the alpha- and beta-selectivity at the anomeric carbon of N-glycosyl

  糖基脲衍生物领域的研究，其中 O-和 N-糖苷键被脲-糖苷键取代，最近随着在氨基糖苷类抗生素领域的应用而出现。我们开发了一种通过 Pd(II) 催化重排糖基三氯乙酰亚胺酯立体选择性合成 α-和 β-糖基脲的新方法。在我们的方法中，N-糖基三氯乙酰胺异头碳的 α 和 β 选择性取决于钯配体催化剂的性质。阳离子 Pd(II)-L-4（2-三氟乙酰苯酚）复合物促进 α 选择性，而中性 Pd(II)-TTMPP-L-5（4-氯-2-三氟乙酰苯酚）复合物则有利于 β 选择性。所得的α-和β-N-糖基三氯乙酰胺进一步与各种初级和受阻二级氮亲核试剂偶联，以中等至良好的产率提供相应的糖基脲，并且在异头碳上没有立体化学完整性的损失。我们进一步证明了 N-糖基三氯乙酰胺作为合成不对称脲连接的二糖和三糖的强大且通用的中间体的效用。
• Exploring Cooperative Effects in Oxidative NHC Catalysis: Regioselective Acylation of Carbohydrates
  作者：David L. Cramer、Srikrishna Bera、Armido Studer

  DOI：10.1002/chem.201601398

  日期：2016.5.23

  The utility of oxidative NHC catalysis for both the regioselective and chemoselective functionalization of carbohydrates is explored. Chiral NHCs allow for the highly regioselective oxidative esterification of various carbohydrates using aldehydes as acylation precursors. The transformation was also shown to be amenable to both cis/trans diol isomers, free amino groups, and selective for specific sugar

  探索了氧化NHC催化对碳水化合物的区域选择性和化学选择性功能化的实用性。手性NHC允许使用醛作为酰化前体对各种碳水化合物进行高度区域选择性的氧化酯化。在竞争实验中，还显示该转化既适合顺式/反式二醇异构体，游离氨基基团，又对特定的糖差向异构体具有选择性。通过使用两种协同作用的NHC催化剂，可以提高酰化反应的效率和区域选择性。该方法的潜力已通过氨基连接的新二糖的区域选择性酰化得到证明。