p-methylphenyl-2,3,4,6-tetra-O-tert-butyldimethylsilyl-1-thio-β-D-glucopyranoside | 178181-79-8

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: p-methylphenyl-2,3,4,6-tetra-O-tert-butyldimethylsilyl-1-thio-β-D-glucopyranoside
• 英文别名: [(2R,3R,4S,5R,6S)-3,5-bis[[tert-butyl(dimethyl)silyl]oxy]-2-[[tert-butyl(dimethyl)silyl]oxymethyl]-6-(4-methylphenyl)sulfanyloxan-4-yl]oxy-tert-butyl-dimethylsilane
• CAS: 178181-79-8
• 化学式: C₃₇H₇₄O₅SSi₄
• 分子量: 743.4
• InChiKey: SFOIASNRRMMEBR-AALIFHQRSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  12.01
• 重原子数：
  47
• 可旋转键数：
  15
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.84
• 拓扑面积：
  71.4
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  p-methylphenyl-2,3,4,6-tetra-O-tert-butyldimethylsilyl-1-thio-β-D-glucopyranoside 在 N-碘代丁二酰亚胺 、 三氟甲磺酸 作用下， 以 辛醇 为溶剂， 生成 1,6-anhydro-2,3,4-tri-O-tert-butyldimethylsilyl-β-D-glucopyranose
  参考文献：
  名称：

  “Super Armed” Glycosyl Donors:  Conformational Arming of Thioglycosides by Silylation

  摘要：

  Glycosyl donors protected with bulky silyl protective groups (tert-butyldimethylsilyl, TBS), on the 2-, 3-, and 4-OH groups were found to have superior reactivity compared with benzylated thioglucosides. The enhanced reactivity is explained by the stereoelectronic effects associated with the conformational change induced by the silylation. A TBS silylated thioglucoside donor has axial OR groups, whereas a benzylated thioglucoside has equatorial OR groups, leading to much more favorable charge-dipole interactions in the transition state. This concept could be used to create "super armed" glucosyl, mannosyl, rhamnosyl, and galactosyl donors, which could cross-couple with the armed acceptors, phenyl 2,3,4-tri-O- benzyl-beta-D-thioglucoside or phenyl 2,3,6-tri-O-benzyl-beta-D-thioglucoside, to give the corresponding armed disaccharides in good to excellent yields.

  DOI：

  10.1021/ja071955l
• 作为产物：
  描述：

  β-D-葡萄糖五乙酸酯 在 吡啶 、 4-二甲氨基吡啶 、 三氟化硼乙醚 作用下， 以 二氯甲烷 为溶剂， 反应 68.5h， 生成 p-methylphenyl-2,3,4,6-tetra-O-tert-butyldimethylsilyl-1-thio-β-D-glucopyranoside
  参考文献：
  名称：

  “Super Armed” Glycosyl Donors:  Conformational Arming of Thioglycosides by Silylation

  摘要：

  Glycosyl donors protected with bulky silyl protective groups (tert-butyldimethylsilyl, TBS), on the 2-, 3-, and 4-OH groups were found to have superior reactivity compared with benzylated thioglucosides. The enhanced reactivity is explained by the stereoelectronic effects associated with the conformational change induced by the silylation. A TBS silylated thioglucoside donor has axial OR groups, whereas a benzylated thioglucoside has equatorial OR groups, leading to much more favorable charge-dipole interactions in the transition state. This concept could be used to create "super armed" glucosyl, mannosyl, rhamnosyl, and galactosyl donors, which could cross-couple with the armed acceptors, phenyl 2,3,4-tri-O- benzyl-beta-D-thioglucoside or phenyl 2,3,6-tri-O-benzyl-beta-D-thioglucoside, to give the corresponding armed disaccharides in good to excellent yields.

  DOI：

  10.1021/ja071955l

文献信息

• Chemoselective deprotection of acid labile primary hydroxyl protecting groups under CBr4-photoirradiation conditions
  作者：Ming-Yi Chen、Laxmikant N. Patkar、Kuo-Cheng Lu、Adam Shih-Yuan Lee、Chun-Cheng Lin

  DOI：10.1016/j.tet.2004.09.095

  日期：2004.12

  The CBr4-photoirradiation in methanol generates a controlled source of HBr, which can chemoselectively deprotect commonly used hydroxyl-protecting groups in saccharides and nucleosides, such as tert-butyldimethylsilyl, isopropylidene, benzylidene and triphenyl ethers in the presence of other acid-labile functional groups. (C) 2004 Elsevier Ltd. All rights reserved.
• Chemoselective deprotection of primary tert-butyldimethylsilyl ethers on carbohydrate molecules in the presence of secondary silyl ethers
  作者：Ming-Yi Chen、Kuo-Cheng Lu、Adam Shih-Yuan Lee、Chun-Cheng Lin

  DOI：10.1016/s0040-4039(02)00385-4

  日期：2002.4

  The primary silyl ethers of TBDMS-protected saccharides were regioselectively cleaved in excellent yields (71-95%) by treating the silyl ethers with a catalytic amount of CBr4 in methanol under photochemical reaction conditions. (C) 2002 Elsevier Science Ltd. All rights reserved.
• “Super Armed” Glycosyl Donors:  Conformational Arming of Thioglycosides by Silylation
  作者：Christian Marcus Pedersen、Lars Ulrik Nordstrøm、Mikael Bols

  DOI：10.1021/ja071955l

  日期：2007.7.1

  Glycosyl donors protected with bulky silyl protective groups (tert-butyldimethylsilyl, TBS), on the 2-, 3-, and 4-OH groups were found to have superior reactivity compared with benzylated thioglucosides. The enhanced reactivity is explained by the stereoelectronic effects associated with the conformational change induced by the silylation. A TBS silylated thioglucoside donor has axial OR groups, whereas a benzylated thioglucoside has equatorial OR groups, leading to much more favorable charge-dipole interactions in the transition state. This concept could be used to create "super armed" glucosyl, mannosyl, rhamnosyl, and galactosyl donors, which could cross-couple with the armed acceptors, phenyl 2,3,4-tri-O- benzyl-beta-D-thioglucoside or phenyl 2,3,6-tri-O-benzyl-beta-D-thioglucoside, to give the corresponding armed disaccharides in good to excellent yields.