2-azido-3,4,6-tri-O-benzyl-2-deoxy-α-D-galactopyranosyl trichloroacetimidate | 94715-55-6

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 2-azido-3,4,6-tri-O-benzyl-2-deoxy-α-D-galactopyranosyl trichloroacetimidate
• 英文别名: 2-azido-3,4,6-tri-O-benzyl-2-deoxy-α-D-galuctopyranosyl trichloroacetimidate；O-(2-deoxy-2-azido-3,4,6-tri-O-benzyl-α-D-galactopyranosyl) trichloroacetimidate；2-azido-3,4,6-tri-O-benzyl-2-deoxy-α-D-galactopyranose 1-O-trichloroacetimidate；[(2R,3R,4R,5R,6R)-3-azido-4,5-bis(phenylmethoxy)-6-(phenylmethoxymethyl)oxan-2-yl] 2,2,2-trichloroethanimidate
• CAS: 94715-55-6
• 化学式: C₂₉H₂₉Cl₃N₄O₅
• 分子量: 619.932
• InChiKey: UNTPMXAMWXTTHZ-IURCNINISA-N

计算性质

• 辛醇/水分配系数(LogP)：
  7
• 重原子数：
  41
• 可旋转键数：
  13
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.34
• 拓扑面积：
  84.4
• 氢给体数：
  1
• 氢受体数：
  8

反应信息

• 作为反应物：
  描述：

  2-azido-3,4,6-tri-O-benzyl-2-deoxy-α-D-galactopyranosyl trichloroacetimidate 在 吡啶 、 三氟甲磺酸三甲基硅酯 、 4 A molecular sieve 、 碳酸氢钠 、 苯硫酚 、 三乙胺 、 间氯过氧苯甲酸 、 tin(ll) chloride 作用下， 以 二氯甲烷 、 乙腈 为溶剂， 反应 3.83h， 生成 2-acetamido-2-deoxy-3,4,6-tri-O-benzyl-D-galactopyranose
  参考文献：
  名称：

  通过螯合控制的C-糖基化立体控制合成α-C-半乳糖胺衍生物。

  摘要：

  在巴比尔条件下，二碘化sa通过酮或醛促进的二碘化mar还原的2-脱氧-2-乙酰氨基七乳糖基吡啶基砜α-5出乎意料地以高收率立体合成了α-C-半乳糖胺衍生物。对于羰基底物，α：β选择性范围为20：1至5：1，对于醛，在C7处观察到约5：1的立体选择性，有利于S-异构体。这些C-糖基化反应的立体化学偏好是通过α-定向异头糖基sa（III）化合物的中间体来解释的，该化合物通过金属离子与C2-乙酰氨基的螯合来稳定。

  DOI：

  10.1021/jo971727h
• 作为产物：
  描述：

  2-叠氮-D-半乳糖四乙酸酯 在 N-溴代丁二酰亚胺(NBS) 、 三氟化硼乙醚 、 水 、 sodium methylate 、 sodium hydride 、 1,8-二氮杂双环[5.4.0]十一碳-7-烯 作用下， 以 甲醇 、 二氯甲烷 、 氯仿 、 N,N-二甲基甲酰胺 、 丙酮 、 mineral oil 为溶剂， 反应 3.5h， 生成 2-azido-3,4,6-tri-O-benzyl-2-deoxy-α-D-galactopyranosyl trichloroacetimidate
  参考文献：
  名称：

  Study of the Stereoselectivity of 2-Azido-2-deoxygalactosyl Donors: Remote Protecting Group Effects and Temperature Dependency

  摘要：

  The stereoselectivity of glycosylation reactions is affected by many factors. Synthesis of 1,2-cis glycosidic linkages (such as a linkages in glucose and galactose like monosaccharides) is challenging due to lack of control of the stereoselectivity. Our systematic study of GalN(3) donors with different combination of protecting groups indicated that acetyl groups at the 3- and 4-positions are particularly important for high alpha-selectivity. Temperature is also recognized as a major factor in control of stereoselectivity. Mechanisms responsible for these experimental results are discussed and explored using computational methods. A remote participation model of the acetyl groups is proposed to explain the directing effects of the acetyl groups.

  DOI：

  10.1021/jo1025157

文献信息

• Glycosylphosphonates of 2-Amino-2-deoxy-aldoses. Synthesis of a Phosphonate Analogue of Lipid X
  作者：Karin Briner、Andrea Vasella

  DOI：10.1002/hlca.19870700516

  日期：1987.8.12

  A preparation of glycosylphosphonates (27, 28, 36, 38, and 39) from 2-azido-2-deoxy-glycoses (26,35, and 37) and the synthesis of the non-isosteric phosphonate analogue 3a of lipid X(2) are described. The 2-azido group was introduced by azidonitration. Treatment of the 1-O-acetyl-2-azido-2-deoxy-β-D-galactopyranose 22 with 1.5-3 equiv. of P(OMe)3 and 1.2-2.5 equiv. of TfOSiMe3 gave mainly recovered

  的制剂glycosylphosphonates的（27，28，36，38，和39，从2-叠氮基-2-脱氧葡糖（）26，35，和37）和非电子等排膦酸酯类似物的合成3A脂质X的（2）进行了说明。通过叠氮化引入2-叠氮基团。用1.5-3当量处理1 - O-乙酰基-2-叠氮基-2-脱氧-β-D-吡喃半乳糖22。P（OMe）3和1.2-2.5当量 TfOSiMe 3的分离得到主要回收的起始原料。在P（OMe）3中作为溶剂，即使在TfOSiMe 3存在下，也可以通过施陶丁格反应获得氨基磷酸二甲酯24。然而，用P（OMe）3和TfOSiMe 3处理苄基化的α-D-半乳糖基-三氯乙酰胺酸酯26，可得到α-和β-D-半乳糖基膦酸酯27和28的1：1混合物，而乙酰化的α -D-葡萄糖-亚氨酸酯35生成α-D-葡萄糖-配置的膦酸酯36。膦酸酯形成的立体选择性与相对容易形成的26和35的氧离子中间体有关。从膦酸
• Simultaneous Regio- and Enantiodifferentiation in Carbohydrate Coupling
  作者：M. Belén Cid、Inés Alonso、Francisco Alfonso、Julia B. Bonilla、Javier López-Prados、Manuel Martín-Lomas

  DOI：10.1002/ejoc.200600125

  日期：2006.9

  The glycosylation of 1,2-trans-diequatorial diols derived from tetrabenzoylated and tetrabenzylated D- and L-chiro-inositol with several glycosyl donors has been investigated. An unprecedented dependence of the regioselectivity on the absolute configuration of the acceptor has been found. However this trend is also modulated by the nature of the protecting groups on both the donor and acceptor, with

  已经研究了衍生自四苯甲酰化和四苄基化 D-和 L-手性肌醇的 1,2-反式二赤道二醇与几个糖基供体的糖基化。已经发现区域选择性对受体绝对构型的前所未有的依赖性。然而，这种趋势也受到供体和受体上保护基团的性质的调节，苯甲酰化受体提供更高水平的区域选择性。大多数结果已通过 DFT 计算得到合理化，这表明供体和受体之间的立体电子因素和氢键决定了它们的相对取向并决定了该过程的区域化学结果。这些研究还强调了与要糖基化的 OH 相邻的酰基在促进糖基化反应中的作用。
• Synthesis of α-D-Gal<i>p</i>N₃-(1-3)-D-Gal<i>p</i>N₃: α- and 3-<i>O-</i>selectivity using 3,4-diol acceptors
  作者：Emil Glibstrup、Christian Marcus Pedersen

  DOI：10.3762/bjoc.14.258

  日期：——

  The motif α-D-GalpNAc-(1-3)-D-GalpNAc is very common in Nature and hence its synthesis highly relevant. The synthesis of its azido precursor has been studied and optimized in terms of steps, yields and selectivity. It has been found that glycosylation of the 3,4-diol acceptor is an advantage over the use of a 4-O-protected acceptor and that both regio- and anomeric selectivity is enhanced by bulky

  α-D-GalpNAc-（1-3）-D-GalpNAc基序在自然界很常见，因此其合成极为相关。已对其叠氮基前体的合成进行了步骤，产率和选择性方面的研究和优化。已经发现3，4-二醇受体的糖基化相对于使用4-O-保护的受体是有利的，并且庞大的6-O-保护基团提高了区域和异头异构体的选择性。受体和供体由共同的结构单元制成，限制了保护性操作，在这种情况下，不可避免的副反应。
• Synthesis of a cell-permeable analogue of a glycosylphosphatidylinositol (GPI) intermediate that is toxic to the living bloodstream form of Trypanosoma brucei
  作者：Arthur Crossman、Terry K. Smith、Michael A.J. Ferguson、John S. Brimacombe

  DOI：10.1016/j.tetlet.2005.08.112

  日期：2005.10

  The synthesis of two cell-permeable analogues related to a GPI intermediate is described for studies with living trypano-somes and human (HeLa) cells. One of the analogues is metabolised by the former GPI pathway and is toxic to the parasite Try-panosoma brucei but not to human cells. (c) 2005 Elsevier Ltd. All rights reserved.
• A highly stereoselective construction of 1,2-trans-β-glycosidic linkages capitalizing on 2-azido-2-deoxy-d-glycosyl diphenyl phosphates as glycosyl donors
  作者：Toshifumi Tsuda、Seiichi Nakamura、Shunichi Hashimoto

  DOI：10.1016/j.tet.2004.08.076

  日期：2004.11

  The scope of TMSOTf-promoted glycosidation of 2-azido-2-deoxyglycopyranosyl diphenyl phosphates is investigated. The 3,4,6-tri-O-benzyl-protected glucosyl and galactosyl donors and the 4,6-O-benzylidene-protected galactosyl donor each react with a range of acceptor alcohols in the presence of a stoichiometric amount of TMSOTf in propionitrile at -78 degreesC to afford 1,2-trans-beta-linked disaccharides in high yields with alpha:beta ratios ranging from 9:91 to 1: > 99, regardless of the anomeric composition of the donor used. The use of propionitrile as a solvent at -78 degreesC has proven to be among the best choice for the highest levels of beta-selectivity reported to date for this type of glycosidation. A plausible reaction mechanism, which features a large equilibrium preference for alpha-glycosyl-nitrilium ions over beta-nitrilium ions, is proposed based on byproducts formed through their intermediacy and accounts for the observed excellent beta-selectivities. (C) 2004 Elsevier Ltd. All rights reserved.