4-tert-butylphenyl 6-O-(tert-butyldimethylsilyl)-2,3-dideoxy-α-D-threo-hex-2-enopyranoside | 201233-06-9

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: 4-tert-butylphenyl 6-O-(tert-butyldimethylsilyl)-2,3-dideoxy-α-D-threo-hex-2-enopyranoside
• 英文别名: p-tert-Butylphenyl 6-O-(tert-butyldimethylsilyl)-2,3-dideoxy-α-D-threo-hex-2-enopyranoside；(2R,3R,6R)-2-[[tert-butyl(dimethyl)silyl]oxymethyl]-6-(4-tert-butylphenoxy)-3,6-dihydro-2H-pyran-3-ol
• CAS: 201233-06-9
• 化学式: C₂₂H₃₆O₄Si
• 分子量: 392.611
• InChiKey: YWOHFCULFXPLEK-AQNXPRMDSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.03
• 重原子数：
  27
• 可旋转键数：
  7
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.64
• 拓扑面积：
  47.9
• 氢给体数：
  1
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  4-tert-butylphenyl 6-O-(tert-butyldimethylsilyl)-2,3-dideoxy-α-D-threo-hex-2-enopyranoside 在 palladium diacetate 四丁基硫酸氢铵 、 sodium hydride 、 三乙胺 、 三苯基膦 作用下， 以 四氢呋喃 、 水 、 乙腈 为溶剂， 反应 79.0h， 生成 1,2,3,4-tetradeoxy-2',3',4',5'-tetrahydro-6-O-(tert-butyldimethylsilyl)-4'-methylene-D-lyxo-hex-1-enopyranoso-[4,3-b]furan
  参考文献：
  名称：

  Palladium-Mediated Cyclization on Carbohydrate Templates. 3. Extension of The Cyclization to the Threo Series.

  摘要：

  The palladium(0)-catalyzed Heck-type cyclization-beta-alkoxy elimination reaction leading to enantiopure bicyclic compounds in the case of erythro 2,3-unsaturated glycosides has been successfully extended to the three stereoisomer by only changing the aglycon moiety from an ethoxy group to an aryloxy moiety.

  DOI：

  10.1080/07328300008544075
• 作为产物：
  描述：

  p-tert-Butylphenyl 6-O-(tert-butyldimethylsilyl)-2,3-dideoxy-α-D-erythro-hex-2-enopyranoside 在 sodium methylate 、 氯乙酸 、 三苯基膦 、 偶氮二甲酸二乙酯 作用下， 生成 4-tert-butylphenyl 6-O-(tert-butyldimethylsilyl)-2,3-dideoxy-α-D-threo-hex-2-enopyranoside
  参考文献：
  名称：

  Synthesis of α- and β-C-Aryl Δ²-Glycopyranosides from p-tert-Butylphenyl Δ²-Glycopyranosides via Grignard Reagents

  摘要：

  Treatment of p-tert-butylphenyl 4,6-di-O-benzyl-2,3-dideoxy-alpha-D-erythro-hex-2-enopyranoside (1a alpha) or the 4,6-di-O-(tert-butyldimethylsilyl) analogue (1b alpha) with various functionalized arylmagnesium bromides in the presence of a catalytic amount of PdCl2(dppf) at 25 degrees C in THF afforded the corresponding unsaturated C-arylglycosides 2-14 having the ct-configuration in quite good yields. Benzyl-, allyl-, and vinylmagnesium bromides gave also the corresponding unsaturated alpha-C-glycosides 15-18, although in lower yields. When the same reaction was performed in the presence of NiCl2(dppe) as the catalyst at -40 degrees C, only the formation of the corresponding unsaturated C-arylglycosides having the beta-configuration was observed. As expected, reaction of phenylmagnesium bromide with p-tert-butylphenyl 4,6-di-O-benzyl-2,3-dideoxy-beta-D-erythro-hex-2-enopyranoside (1a beta) in the presence of NiCl2(dppe) gave only the unsaturated beta-C-phenylglycoside 2a beta, while palladium-catalyzed reaction led to the preponderant formation of C-phenylglycoside 2a alpha. Reaction of PhMgBr with p-tert-butylphenyl 4-O-benzyl-2,3,6-trideoxy-alpha-L-erythro-hex-2-enopyranoside (20) afforded stereospecifically the unsaturated alpha- and beta-C-phenylglycoside 25 in the presence of PdCl2-(dppf) and NiCl2(dppe), respectively.

  DOI：

  10.1021/jo9714674

文献信息

• Intramolecular Heck Cyclisation-β-Alkoxy Elimination in Carbohydrate Chemistry. A Simple Route to Enantiopure Annelated Dioxatricyclic Compounds
  作者：Karim Bedjeguelal、Véronique Bolitt、Denis Sinou

  DOI：10.1055/s-1999-2717

  日期：1999.6

  Enantiopure cis-fused pyrano[2,3c]pyrans are obtained from glycals via an intramolecular Heck cyclization followed by a palladium-β-alkoxy elimination.

  通过分子内 Heck 环化反应和钯-δ-烷氧基消除反应，从甘氨酸中获得了不纯的顺式融合吡喃并[2,3c]吡喃。
• Palladium-Mediated Cyclization on Carbohydrate Templates Synthesis of Enantiopure Annelated Tricyclic Compounds
  作者：Denis Sinou、Karim Bedjeguelal

  DOI：10.1002/1099-0690(200012)2000:24<4071::aid-ejoc4071>3.0.co;2-1

  日期：2000.12

  using the same methodology as for 2, after inversion of configuration at C-4 by means of a Mitsunobu reaction. Treatment of the unsaturated carbohydrates 2−4, 6−8, and 10 with a catalytic amount of Pd(OAc)2/PPh3 in DMF in the presence of Bu4NHSO4 and NEt3 afforded the annelated tricyclic compounds 11−13 and 15−18 in good yields when the anomeric substituent was the p-tert-butylphenyl group, via an intramolecular

  各种溴不饱和碳水化合物 2-4 已从乙基和芳基 4,6-di-O-acetyl-2,3-dideoxy-α-D-erythro-hex-2-enopyranoside 通过脱乙酰作用制备，然后首先用 TBDMSCl 进行单甲硅烷基化然后用2-溴苄基溴或1-溴-溴甲基环烯烃烷基化。N-、C-和 O-类似物 6-8 是通过钯介导的碳酸盐 5 与 TsNHCH2-C6H4-o-Br、(CO2Me)2CH-C6H4-o-Br 和 HOC6H4-oI 的烷基化制备的，分别。苏式类似物 10 使用与 2 相同的方法获得，在 C-4 处通过 Mitsunobu 反应反转构型之后。不饱和碳水化合物2-4、6-8的处理，
• Synthesis of α- and β-<i>C</i>-Aryl Δ²-Glycopyranosides from <i>p</i>-<i>tert</i>-Butylphenyl Δ²-Glycopyranosides via Grignard Reagents
  作者：Christophe Moineau、Véronique Bolitt、Denis Sinou

  DOI：10.1021/jo9714674

  日期：1998.2.1

  Treatment of p-tert-butylphenyl 4,6-di-O-benzyl-2,3-dideoxy-alpha-D-erythro-hex-2-enopyranoside (1a alpha) or the 4,6-di-O-(tert-butyldimethylsilyl) analogue (1b alpha) with various functionalized arylmagnesium bromides in the presence of a catalytic amount of PdCl2(dppf) at 25 degrees C in THF afforded the corresponding unsaturated C-arylglycosides 2-14 having the ct-configuration in quite good yields. Benzyl-, allyl-, and vinylmagnesium bromides gave also the corresponding unsaturated alpha-C-glycosides 15-18, although in lower yields. When the same reaction was performed in the presence of NiCl2(dppe) as the catalyst at -40 degrees C, only the formation of the corresponding unsaturated C-arylglycosides having the beta-configuration was observed. As expected, reaction of phenylmagnesium bromide with p-tert-butylphenyl 4,6-di-O-benzyl-2,3-dideoxy-beta-D-erythro-hex-2-enopyranoside (1a beta) in the presence of NiCl2(dppe) gave only the unsaturated beta-C-phenylglycoside 2a beta, while palladium-catalyzed reaction led to the preponderant formation of C-phenylglycoside 2a alpha. Reaction of PhMgBr with p-tert-butylphenyl 4-O-benzyl-2,3,6-trideoxy-alpha-L-erythro-hex-2-enopyranoside (20) afforded stereospecifically the unsaturated alpha- and beta-C-phenylglycoside 25 in the presence of PdCl2-(dppf) and NiCl2(dppe), respectively.
• Palladium-Mediated Cyclization on Carbohydrate Templates. 3. Extension of The Cyclization to the Threo Series.
  作者：Karim Bedjeguelal、Laure Joseph、Véronique Bolitt、Denis Sinou

  DOI：10.1080/07328300008544075

  日期：2000.1

  The palladium(0)-catalyzed Heck-type cyclization-beta-alkoxy elimination reaction leading to enantiopure bicyclic compounds in the case of erythro 2,3-unsaturated glycosides has been successfully extended to the three stereoisomer by only changing the aglycon moiety from an ethoxy group to an aryloxy moiety.