3-C-(2-O-acetyl-3,4,6-tri-O-benzyl-β-D-glycopyranosyl)propene | 193546-84-8

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 3-C-(2-O-acetyl-3,4,6-tri-O-benzyl-β-D-glycopyranosyl)propene
• 英文别名: [(2S,3S,4S,5R,6R)-4,5-bis(phenylmethoxy)-6-(phenylmethoxymethyl)-2-prop-2-enyloxan-3-yl] acetate
• CAS: 193546-84-8
• 化学式: C₃₂H₃₆O₆
• 分子量: 516.634
• InChiKey: UEPHPANXDZZLFN-VYDZHMBASA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.2
• 重原子数：
  38
• 可旋转键数：
  14
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.34
• 拓扑面积：
  63.2
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  3-C-(2-O-acetyl-3,4,6-tri-O-benzyl-β-D-glycopyranosyl)propene 在 sodium methylate 作用下， 以 甲醇 为溶剂， 反应 2.0h， 以91%的产率得到3-(3,4,6-tri-O-benzyl-β-D-glucopyranosyl)-1-propene
  参考文献：
  名称：

  Multifunctionalized α,β-cyclopentenones from C-2 and C-4-ulopyranosyl compounds: a stereospecific rearrangement initiated by base

  摘要：

  Base treatment of O-benzyl protected C-2- or C-4-ulopyranosyl compounds (4 alpha, 4 beta, and 11) by either 10% Et3N or 1% K2CO3 in MeOH initiated a beta elimination to afford alpha,beta-unsaturated C-ulopyranosyl compounds (5 alpha, 5 beta, and 12), which further rearranged in a stereocontrolled manner to multifuctionalized alpha,beta-cyclopentenones (6 and 14) in 70-80% yield. Both C-alpha- and C-beta-2-ulosides (5 alpha and 5 beta) produced the same cyclopentenone 6, indicating that a 1,2-enolate is formed prior to the cleavage of the C-5-O bond. Because 6 is racemic, it was probably formed by the intramolecular cycloaldolization of two equally populated enantiomeric intermediates. When treated with 90% Et3N in MeOH, 5 alpha yielded almost exclusively 15 (isomer of 6), which was formed by a migration of the double bond in 5 alpha during the previously described rearrangement. Thus either 6 or 15 was the major product, depending on the base used. (C) 2001 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0008-6215(01)00187-2
• 作为产物：
  描述：

  (3R,4R,5S)-4,5-Bis-benzyloxy-3-benzyloxymethyl-2,7-dioxa-bicyclo[4.1.0]heptane 在 吡啶 作用下， 以 乙醚 为溶剂， 生成 3-C-(2-O-acetyl-3,4,6-tri-O-benzyl-β-D-glycopyranosyl)propene
  参考文献：
  名称：

  Cytotoxic effects of C-glycosides in HOS and HeLa cell lines

  摘要：

  Fifty-two C-glycosides were synthesized and their in-vitro antiproliferative activity screened against human cervical carcinoma (HeLa) and osteosarcoma (HOS) cell lines. Nine of them had growth inhibitions (GI(50) values) below 10 mu M, the Gglucopyranoside 38 being the most active against HeLa (5.4 mu M) and the dichlorocyclopropyl derivative 42 against HOS (1.6 mu M). Some preliminary structure-activity relationships were established. (c) 2007 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.bmcl.2007.04.060

文献信息

• C-Glycosides to Fused Polycyclic Ethers. A Formal Synthesis of (±)-Hemibrevetoxin B
  作者：Jon D. Rainier、Shawn P. Allwein、Jason M. Cox

  DOI：10.1021/jo001514j

  日期：2001.2.1

  This paper describes a formal total synthesis of the marine ladder toxin hemibrevetoxin B from Danishefsky's dienes. This approach couples the generation of C-glycosides from cyclic enol ethers with metathesis or acid-mediated annulation reactions. The result is a highly efficient synthesis of the tetracyclic ring system of hemibrevetoxin B.

  本文描述了由Danishefsky的二烯正式合成的海洋梯状毒素半纤维素毒素B。这种方法将环烯醇醚的C-糖苷的生成与复分解或酸介导的环化反应结合在一起。结果是高效合成半短毒素B的四环系统。
• The Synthesis of Some Epoxyalkyl b-C-Glycosides as Potential Inhibitors of b-Glucan Hydrolases
  作者：Wayne M. Best、Vito Ferro、Julia Harle、Robert V. Stick、D. Matthew G. Tilbrook

  DOI：10.1071/c97015

  日期：——

  The treatment of tetra-O-benzyl-D-glucono-1,5-lactone with various alkenylmagnesium halides gave the intermediate lactols which, upon reduction (Et3SiH/BF3) and protecting group manipulation, yielded alkenyl tetra-O-acetyl-β-D-C-glucopyranosides in good yield. These β-D-C-glucosides were precursors of the epoxyalkyl β-D-C-glucopyranosides, themselves putative inhibitors of b-glucan hydrolases. Similar additions of Grignard reagents to per-benzylated cellobionolactone were not as successful in yielding epoxyalkyl β-C-cellobiosides. The addition of Grignard reagents to 1,2-anhydro-3,4,6-tri-O-benzyl-α-D- glucose offers a viable alternative route to the prop-2-enyl β-D-C-glucoside, but not to the but-3-enyl and pent-4-enyl counterparts. Likewise, the addition of Grignard reagents to a 1,2-anhydro cellobiose gave disappointing results. Preliminary results are reported for a novel approach to alkenyl β-D-C-glucosides by the alkylation of nitromethyl β-D-C-glucosides.

  用各种烯基卤化镁处理四-O-苄基-D-葡萄糖醛酸-1,5-内酯，可以得到中间内酯。 与各种烯基卤化镁处理后得到中间体内酯、 经还原（Et3SiH/BF3） 和保护基操作后，得到烯基 四-O-乙酰基-β-D-C-吡喃葡萄糖苷 产量很高。这些β-D-C-吡喃葡萄糖苷是 环氧烷基 β-D-C-吡喃葡萄糖苷的前体、 这些β-D-C-吡喃葡萄糖苷是环氧烷基β-D-C-吡喃葡萄糖苷的前体。类似的 格氏试剂的效果并不理想。 生成环氧烷基 β-C-纤维二糖苷。在 格氏试剂添加到 1,2-脱水-3,4,6-三-O-苄基-α-D-葡萄糖提供了 丙-2-烯基-β-D-葡萄糖的一种可行的替代途径。 β-D-C-葡萄糖苷提供了可行的替代途径，但并没有提供丁-3-烯基和 戊-4-烯基的对应物。同样，将格氏试剂加入到 1,2-anhydro cellobiose 的结果令人失望。初步结果 报告了烯基 β-D-C-葡萄糖苷的新方法的初步结果。 β-D-C-葡萄糖苷的新方法的初步结果。
• C-Glycosides to fused polycyclic ethers
  作者：Shawn P. Allwein、Jason M. Cox、Brett E. Howard、Henry W.B. Johnson、Jon D. Rainier

  DOI：10.1016/s0040-4020(02)00057-1

  日期：2002.3

  This manuscript describes the synthesis of fused polycyclic ethers from the coupling of C-glycoside forming reactions with ring closing metathesis and acid mediated annulation reactions. (C) 2002 Elsevier Science Ltd. All rights reserved.
• An Iterative Approach to Fused Ether Ring Systems
  作者：Jon D. Rainier、Shawn P. Allwein

  DOI：10.1021/jo980996k

  日期：1998.8.1
• Olefinic Ester and Diene Ring-Closing Metathesis Using a Reduced Titanium Alkylidene
  作者：Karthik Iyer、Jon D. Rainier

  DOI：10.1021/ja073880r

  日期：2007.10.1

  This manuscript describes the use of a reduced titanium ethylidene reagent in olefinic ester cyclization reactions and diene RCM reactions.