1,2,3,4-tetradeoxy-2',3',4',5'-tetrahydro-6-O-(tert-butyldimethylsilyl)-4'-methylene-D-ribo-hex-1-enopyranoso-[4,3-b]furan

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 呋喃吡喃类
• 英文名称: 1,2,3,4-tetradeoxy-2',3',4',5'-tetrahydro-6-O-(tert-butyldimethylsilyl)-4'-methylene-D-ribo-hex-1-enopyranoso-[4,3-b]furan
• 英文别名: [(3aR,7R,7aS)-3-methylidene-7,7a-dihydro-3aH-furo[2,3-c]pyran-7-yl]methoxy-tert-butyl-dimethylsilane
• 化学式: C₁₅H₂₆O₃Si
• 分子量: 282.455
• InChiKey: IHDCLLTZPSBFGP-MCIONIFRSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.49
• 重原子数：
  19
• 可旋转键数：
  4
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.73
• 拓扑面积：
  27.7
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为产物：
  描述：

  ethyl 6-O-tert-butyldimethylsilyl-4-hydroxyl-2,3-dideoxy-α-D-erythro-hex-2-enopyranoside 在 palladium diacetate 、 sodium formate 、 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 14.0h， 生成 1,2,3,4-tetradeoxy-2',3',4',5'-tetrahydro-6-O-(tert-butyldimethylsilyl)-4'-methylene-D-ribo-hex-1-enopyranoso-[4,3-b]furan
  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

• An unexpected palladium-catalysed cyclisation on carbohydrate templates
  作者：Jean-Flaubert Nguefack、V�ronique Bolitt、Denis Sinou

  DOI：10.1039/c39950001893

  日期：——

  Alkyl 4-O-bromoalkenyl α-Δ2-glycopyranosides 1 undergo a palladium-mediated Heck-type cyclisation providing bicyclic glycals 4 in good yields via a syn-dealkoxypalladation pathway.

  烷基-4- ø -bromoalkenylα-Δ 2个-glycopyranosides 1经历钯介导的Heck型环化提供双环烯糖4以良好的收率通过一个SYN -dealkoxypalladation通路。
• Palladium-mediated cyclisation on carbohydrate templates A new route to bis-annulated pyranosides
  作者：Jean-Flaubert Nguefack、Véronique Bolitt、Denis Sinou

  DOI：10.1016/0040-4039(95)02096-9

  日期：1996.1

  A new and efficient route to bis-annulated pyranosides by palladium(0)-catalysed cascade cyclisation is described. The appropriate 2,3-unsaturated allylglycosides are subjected to Heck reaction under smooth Jeffery's conditions to produce the tricyclic derivatives in good yields.

  描述了一种新的有效途径，通过钯（0）催化的级联环化反应生成双环吡喃糖苷。合适的2，3-不饱和烯丙基糖苷在光滑的Jeffery条件下进行Heck反应，以高收率生产三环衍生物。
• Palladium-Mediated Cyclization on Carbohydrate Templates. 2. Synthesis of Enantiopure Tricyclic Compounds
  作者：Jean-Flaubert Nguefack、Véronique Bolitt、Denis Sinou

  DOI：10.1021/jo970817j

  日期：1997.10.1

  The bromo substituted unsaturated carbohydrates 3a-f were prepared from 3,4,6-tri-O-acetyl-D-glucal by Ferrier reaction with the appropriate allylic or homoallylic alcohol, deacetylation followed by monosilylation with TBDMSCl, and then alkylation with BrCH2CBr=CH2. The N- and C-analogues 4a,b were synthesized by palladium alkylation of the intermediate carbonate with TsNHCH2CBr=CH2 and (MeO2C)(2)CHCH2CBr=CH2, respectively. Treatment of the unsaturated carbohydrates 3a, 4a, and 4b with a catalytic amount of Pd(OAc)(2)/PPh3 in CH3CN/H2O, in the presence of Bu4NHSO4 and NEt3, afforded the tricyclic compounds 5, 6, and 7, respectively. Under the same conditions, the analogue tricyclic compounds 8, 9, and 10 were formed starting from 3b-d. In the case of compounds 3e and 3f, the formation of the bicyclic glucal 11 via an already described beta-alkoxyelimination was only observed. Moreover, trapping of the sigma-alkylpalladium intermediate obtained from 3e with an external nucleophile yielded the 2-deoxy carbohydrate 12 and the 2,3-unsaturated sugar 13, using respectively sodium formate and sodium tetraphenylborate.
• 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.
• 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.