phenyl 2-deoxy-2-phthalimido-1-thio-β-D-galactopyranoside | 362614-07-1

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: phenyl 2-deoxy-2-phthalimido-1-thio-β-D-galactopyranoside
• 英文别名: phenyl 2-deoxy-2-phthalimide-1-thio-β-D-galactopyranoside；2-[(2S,3R,4R,5R,6R)-4,5-dihydroxy-6-(hydroxymethyl)-2-phenylsulfanyloxan-3-yl]isoindole-1,3-dione
• CAS: 362614-07-1
• 化学式: C₂₀H₁₉NO₆S
• 分子量: 401.44
• InChiKey: HLTWBWIHWDQQFB-XDCWJTEKSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.7
• 重原子数：
  28
• 可旋转键数：
  4
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.3
• 拓扑面积：
  133
• 氢给体数：
  3
• 氢受体数：
  7

反应信息

• 作为反应物：
  描述：

  phenyl 2-deoxy-2-phthalimido-1-thio-β-D-galactopyranoside 在 吡啶 、 二正丁基氧化锡 作用下， 以 甲醇 为溶剂， 反应 14.0h， 生成 phenyl 4,6-di-O-acetyl-2-deoxy-3-O-p-methoxybenzyl-2-phthalimido-1-thio-β-D-galactopyranoside
  参考文献：
  名称：

  A HIGHLY EFFICIENT TOTAL SYNTHETIC ROUTE TO α-SERIES GANGLIOSIDES: GM1α, GD1α, AND GT1α1-2

  摘要：

  A highly efficient total synthetic route to alpha -series gangliosides GM1 alpha, GD1 alpha and GT1 alpha is described. The suitably protected gangliotriose (GgOse3) derivatives, i.e., 2-(trimethylsilyl)ethyl (2-acetamido-2-deoxy-3-O-p-methoxybenzyl-beta -D-galactopyranosyl)-(1-->4)-(2,3,6-tri-O-benzyl-beta -D-galactopyranosyl)-(1 -->4)-2,3,6-tri-O-benzyl-beta -D-glucopyranoside (8) and the corresponding III3-levulinoyl derivative (9), were regioselectively glycosylated with the phenyl 2-thioglycoside of N-acetylneuraminic acid (Neu5Ac) promoted by N-iodosuccinimide (NIS)-trimethylsilyl trifluoromethanesulfonate (TMSOTf) or trifluoromethanesulfonic acid (TfOH) in acetonitrile, to give the desired alpha -Neu5Ac-(2-->6)-gangliotriose (III(6)Neu5AcGgOse3) derivatives as the major products (11 and 12). The p-methoxybenzyl (MPM) group in 11 or the levulinoyl group in 12 was selectively removed, and the resulting 2-(trimethylsilyl)ethyl (methyl 5-acetamido-4,7,8,9-tetra-O-acetyl-3,5-dideoxy-D-glycero-alpha -D-galacto-2-nonulopyranosylonate)-(2-->6)-(2-acetamido-2-deoxy-beta -D-galactopyranosyl)-(1-->4)-(2,3,6-tri-O-benzyl-beta -D-galactopyranosyl)-(1-->4)-2,3,6-tri-O-benzyl-beta -D-glucopyranoside (13), a key glycosyl acceptor, was systematically glycosylated with the galactose donor (14), alpha -Neu5Ac-(2-->3)-galactuse donor (15) and alpha -Neu5Ac-(2-->8)-alpha -Neu5Ac-(2-->3)-galactose donor (20) to give the protected GM1 alpha (16, 70%), GD1 alpha (17, 80%) and GT1 alpha (21, 87%) oligosaccharides, respectively, which can be converted to the target gangliosides by the introduction of ceramide and then complete deprotection.

  DOI：

  10.1081/car-100103959
• 作为产物：
  描述：

  phenyl 3,4,6-tri-O-acetyl-2-deoxy-2-phthalimido-1-thio-β-D-galactopyranoside 在 甲醇 、 sodium methylate 作用下， 生成 phenyl 2-deoxy-2-phthalimido-1-thio-β-D-galactopyranoside
  参考文献：
  名称：

  通过立体特异性、化学选择性脱氨作用实现唾液酸糖苷的化学多样化

  摘要：

  大器晚成：全乙酰化的唾液酸糖苷的亚硝化，接着用三氟乙醇钠处理，然后合适的亲核使这些甙与立体有择更换乙酰胺基的后期阶段修饰。这种方法应该能够以最少的合成工作获得许多糖苷衍生物。

  DOI：

  10.1002/anie.201303781

文献信息

• The Origin of High Stereoselectivity in Di-<i>tert</i>-butylsilylene-Directed α-Galactosylation
  作者：Akihiro Imamura、Naomi Matsuzawa、Shizuo Sakai、Taro Udagawa、Shinya Nakashima、Hiromune Ando、Hideharu Ishida、Makoto Kiso

  DOI：10.1021/acs.joc.6b01685

  日期：2016.10.7

  an oxocarbenium ion; (2) a galacto-type glycosyl donor with a cyclic protecting group bridging O4 and O6 to form a six-membered ring; (3) through-space electron donation from O4 and O6 into the empty p-orbital of the anomeric carbon to stabilize the oxocarbenium intermediate; (4) steric hindrance due to bulky alkyl substituents on the cyclic protecting group to prevent nucleophilic attack from the

  已通过实验和计算方法阐明了半乳糖基和半乳糖胺基供体与具有多个亲核试剂的二叔丁基亚甲硅烷基（DTBS）基团反应中的高α（1,2-顺式）-立体选择性的起源。DTBS克服了迄今为止检查的任何其他环状保护基团以及由于CO基团在C2附近的参与而导致的β（1,2-反式）导向作用。对α（1,2-顺式）-立体选择性的要求如下：（1）氧碳鎓离子的产生；（2）具有环保护基团的半乳糖型糖基供体，该保护基桥接O 4和O 6形成六元环；（3）从O4和O6向空p中的空间电子捐赠-异头碳的轨道，以稳定氧碳en中间体；（4）由于在环状保护基上的庞大的烷基取代基而引起的空间位阻，以防止从β-面的亲核攻击。（5）4，6- O-亚甲硅烷基结构。此外，发现在所研究的各种环状保护基团中，DTBS基团的强立体定向作用是独特的和特异性的。
• Sarkar, Sujit Kumar; Roy, Nirmolendu, Indian Journal of Chemistry - Section B Organic and Medicinal Chemistry, 2004, vol. 43, # 11, p. 2386 - 2394
  作者：Sarkar, Sujit Kumar、Roy, Nirmolendu

  DOI：——

  日期：——
• A HIGHLY EFFICIENT TOTAL SYNTHETIC ROUTE TO α-SERIES GANGLIOSIDES: GM1α, GD1α, AND GT1α1-2
  作者：Hiromi Ito、Hideharu Ishida、Makoto Kiso

  DOI：10.1081/car-100103959

  日期：2001.3.31

  A highly efficient total synthetic route to alpha -series gangliosides GM1 alpha, GD1 alpha and GT1 alpha is described. The suitably protected gangliotriose (GgOse3) derivatives, i.e., 2-(trimethylsilyl)ethyl (2-acetamido-2-deoxy-3-O-p-methoxybenzyl-beta -D-galactopyranosyl)-(1-->4)-(2,3,6-tri-O-benzyl-beta -D-galactopyranosyl)-(1 -->4)-2,3,6-tri-O-benzyl-beta -D-glucopyranoside (8) and the corresponding III3-levulinoyl derivative (9), were regioselectively glycosylated with the phenyl 2-thioglycoside of N-acetylneuraminic acid (Neu5Ac) promoted by N-iodosuccinimide (NIS)-trimethylsilyl trifluoromethanesulfonate (TMSOTf) or trifluoromethanesulfonic acid (TfOH) in acetonitrile, to give the desired alpha -Neu5Ac-(2-->6)-gangliotriose (III(6)Neu5AcGgOse3) derivatives as the major products (11 and 12). The p-methoxybenzyl (MPM) group in 11 or the levulinoyl group in 12 was selectively removed, and the resulting 2-(trimethylsilyl)ethyl (methyl 5-acetamido-4,7,8,9-tetra-O-acetyl-3,5-dideoxy-D-glycero-alpha -D-galacto-2-nonulopyranosylonate)-(2-->6)-(2-acetamido-2-deoxy-beta -D-galactopyranosyl)-(1-->4)-(2,3,6-tri-O-benzyl-beta -D-galactopyranosyl)-(1-->4)-2,3,6-tri-O-benzyl-beta -D-glucopyranoside (13), a key glycosyl acceptor, was systematically glycosylated with the galactose donor (14), alpha -Neu5Ac-(2-->3)-galactuse donor (15) and alpha -Neu5Ac-(2-->8)-alpha -Neu5Ac-(2-->3)-galactose donor (20) to give the protected GM1 alpha (16, 70%), GD1 alpha (17, 80%) and GT1 alpha (21, 87%) oligosaccharides, respectively, which can be converted to the target gangliosides by the introduction of ceramide and then complete deprotection.
• Chemical Diversification of Sialic Acid Glycosides by Stereospecific, Chemoselective Deamination
  作者：Chandrasekhar Navuluri、David Crich

  DOI：10.1002/anie.201303781

  日期：2013.10.18

  Late bloomer: Nitrosation of peracetylated sialic acid glycosides followed by treatment with sodium trifluoroethoxide and then a suitable nucleophile enables the late‐stage modification of these glycosides with stereospecific replacement of the acetamido group. This method should enable access to many glycoside derivatives with a minimum of synthetic effort.

  大器晚成：全乙酰化的唾液酸糖苷的亚硝化，接着用三氟乙醇钠处理，然后合适的亲核使这些甙与立体有择更换乙酰胺基的后期阶段修饰。这种方法应该能够以最少的合成工作获得许多糖苷衍生物。