[(2R,3R,6S)-3-(2-bromoprop-2-enoxy)-6-ethoxy-3,6-dihydro-2H-pyran-2-yl]methoxy-tert-butyl-dimethylsilane | 187990-49-4

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡喃
• 英文名称: [(2R,3R,6S)-3-(2-bromoprop-2-enoxy)-6-ethoxy-3,6-dihydro-2H-pyran-2-yl]methoxy-tert-butyl-dimethylsilane
• CAS: 187990-49-4
• 化学式: C₁₇H₃₁BrO₄Si
• 分子量: 407.42
• InChiKey: NKFVVCPACZJNSN-OAGGEKHMSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.62
• 重原子数：
  23
• 可旋转键数：
  9
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.76
• 拓扑面积：
  36.9
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  [(2R,3R,6S)-3-(2-bromoprop-2-enoxy)-6-ethoxy-3,6-dihydro-2H-pyran-2-yl]methoxy-tert-butyl-dimethylsilane 在 palladium diacetate 、 四丁基硫酸氢铵 、 三乙胺 、 三苯基膦 作用下， 以 水 、 乙腈 为溶剂， 反应 24.0h， 以57%的产率得到(1R)-2-[tert-butyl(dimethyl)silyl]oxy-1-[(2R,3S)-3-[(E)-2-ethoxyethenyl]-4-methylideneoxolan-2-yl]ethanol
  参考文献：
  名称：

  Palladium-Mediated Cyclization on Carbohydrate Templates. 1. Synthesis of Enantiopure Bicyclic Compounds

  摘要：

  The bromo unsaturated carbohydrates 30 and 9 were prepared from ethyl 4,6-di-O-acetyl-2,3-dideoxy-D-erythro-hex-2-enopyranoside (1a) and (7) by deacetylation followed by monosilylation with TBDMSCl and then alkylation with BrCH2CBr=CH2. The three analogues 6 and 10 were obtained using the same methodology after inversion at C-4 via a Mitsunobu reaction. The N- and C-analogues 4b and 5 were prepared by palladium alkylation of the carbonate 2d with TsNHCH(2)CBr=CH2 and (CO(2)Me)(2)CHCH2CBr=CH2, respectively. Treatment of the unsaturated carbohydrates 3a and 9 with a catalytic amount of Pd(OAc)(2)/PPh(3) in CH3CN/H2O in the presence of Bu(4)NHSO(4) and NEt(3) afforded the bicyclic compound 14a. The N- and C-analogues 14b and 14c were obtained using the same conditions and starting, respectively, from 4b and 5. On the other hand, treatment of the three derivatives 6 and 10 under these conditions gave the furanic structure 15. In the case of compound 30, performing the reaction in the presence of sodium formate yielded the bicyclic 2-deoxy carbohydrate 17.

  DOI：

  10.1021/jo961881o
• 作为产物：
  描述：

  ethyl 4,6-di-O-acetyl-2,3-dideoxy-α-D-erythrohex-2-enopyranoside 在 咪唑 、 sodium methylate 、 sodium hydride 、 三乙胺 、 三苯基膦 、 偶氮二甲酸二乙酯 作用下， 以 四氢呋喃 、 甲醇 、 二氯甲烷 为溶剂， 反应 82.75h， 生成 [(2R,3R,6S)-3-(2-bromoprop-2-enoxy)-6-ethoxy-3,6-dihydro-2H-pyran-2-yl]methoxy-tert-butyl-dimethylsilane
  参考文献：
  名称：

  Palladium-Mediated Cyclization on Carbohydrate Templates. 1. Synthesis of Enantiopure Bicyclic Compounds

  摘要：

  The bromo unsaturated carbohydrates 30 and 9 were prepared from ethyl 4,6-di-O-acetyl-2,3-dideoxy-D-erythro-hex-2-enopyranoside (1a) and (7) by deacetylation followed by monosilylation with TBDMSCl and then alkylation with BrCH2CBr=CH2. The three analogues 6 and 10 were obtained using the same methodology after inversion at C-4 via a Mitsunobu reaction. The N- and C-analogues 4b and 5 were prepared by palladium alkylation of the carbonate 2d with TsNHCH(2)CBr=CH2 and (CO(2)Me)(2)CHCH2CBr=CH2, respectively. Treatment of the unsaturated carbohydrates 3a and 9 with a catalytic amount of Pd(OAc)(2)/PPh(3) in CH3CN/H2O in the presence of Bu(4)NHSO(4) and NEt(3) afforded the bicyclic compound 14a. The N- and C-analogues 14b and 14c were obtained using the same conditions and starting, respectively, from 4b and 5. On the other hand, treatment of the three derivatives 6 and 10 under these conditions gave the furanic structure 15. In the case of compound 30, performing the reaction in the presence of sodium formate yielded the bicyclic 2-deoxy carbohydrate 17.

  DOI：

  10.1021/jo961881o

文献信息

• Aglycon directed palladium β-alcoxyelimination on carbohydrate templates
  作者：Karim Bedjeguelal、Laure Joseph、Véronique Bolitt、Denis Sinou

  DOI：10.1016/s0040-4039(98)80026-9

  日期：1999.1

  The palladium(0)-catalyzed Heck-type cyclisation reaction of erythro or three aryl 2,3-unsaturated glycosides gave the enantiopure bicyclic compounds in quite good yields via a palladium beta-alcoxyelimination. (C) 1998 Elsevier Science Lid. All rights reserved.