ethyl (E)-[3-O-benzyl-5,6-dideoxy-1,2-O-isopropylidene-α-D-gluco]-heptofuran-5-en-uronate | 108788-49-4

• 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: ethyl (E)-[3-O-benzyl-5,6-dideoxy-1,2-O-isopropylidene-α-D-gluco]-heptofuran-5-en-uronate
• 英文别名: (E)-ethyl-(3-O-benzyl-5,6-dideoxy-1,2-O-isopropylidene)-α-D-1,4-heptofuranosyl-5-enoate；(E)-ethyl-1,2-O-isopropylidene-3-O-benzyl-5,6-dideoxy-α-D-xylo-5-eno-heptofuranuronate；ethyl 3-O-benzyl-5,6-dideoxy-1,2-O-isopropylidene-α-D-xylo-5(E)-eno-heptofuranuronoate；ethyl (5E)-3-O-Benzyl-5,6-dideoxy-1,2-O-isopropylidene-α-D-xylo-hept-6-enofuranuroate；ethyl (E)-3-O-benzyl-1,2-O-isopropylidene-5,6-dideoxy-α-D-xylo-5-enoheptofuranuronate；ethyl [3-O-benzyl-5,6-dideoxy-1,2-O-isopropylidene-α-D-gluco]-heptofuran-5-en-uronate；ethyl (E)-3-[(3aR,5R,6S,6aR)-2,2-dimethyl-6-phenylmethoxy-3a,5,6,6a-tetrahydrofuro[2,3-d][1,3]dioxol-5-yl]prop-2-enoate
• CAS: 108788-49-4
• 化学式: C₁₉H₂₄O₆
• 分子量: 348.396
• InChiKey: QKUAHWSYIPGNSW-BKXKVBGLSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.2
• 重原子数：
  25
• 可旋转键数：
  7
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.53
• 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：

  ethyl (E)-[3-O-benzyl-5,6-dideoxy-1,2-O-isopropylidene-α-D-gluco]-heptofuran-5-en-uronate 在 二异丁基氢化铝 作用下， 以 四氢呋喃 为溶剂， 反应 2.0h， 以93%的产率得到3-O-benzyl-5,6-dideoxy-1,2-dideoxy-1,2-O-isopropylidene-α-D-xylohept-5-eno-1,4-furanose
  参考文献：
  名称：

  Synthesis of azepane and nojirimycin iminosugars: the Sharpless asymmetric epoxidation of d-glucose-derived allyl alcohol and highly regioselective epoxide ring opening using sodium azide

  摘要：

  The Sharp less asymmetric epoxidation of D-glucose-derived ally! alcohol 4 afforded alpha- and beta-epoxides 5a and 5b in high stereoselectivity. The epoxide ring opening in 5a/5b was studied with different nucleophilic azido reagents, under various reaction conditions, and was found to be highly regioselective to give the preferential formation of 6-azido diol 6a/6b over 5-azido-diol 7a/7b. The 6-azido diol 6a/6b and 5-azido dial 7a/7b thus obtained were converted to the corresponding seven- and six-membered iminosugar, namely, azepane 1a/1b and 1-deoxy-nojirimycin 2a/2b. (C) 2010 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetasy.2010.01.007
• 作为产物：
  描述：

  3-O-苄基-1,2-O-异亚丙基-Alpha-D-木质二醛糖 、 二氯乙酸乙酯 在 chromium dichloride 作用下， 以 四氢呋喃 为溶剂， 反应 3.0h， 以87%的产率得到ethyl (E)-[3-O-benzyl-5,6-dideoxy-1,2-O-isopropylidene-α-D-gluco]-heptofuran-5-en-uronate
  参考文献：
  名称：

  铬介导的碳水化合物衍生的（E）-α，β-不饱和酯或酰胺的立体选择性合成

  摘要：

  据报道，铬介导的由碳水化合物衍生的二和三取代的（E）-α，β-不饱和酯或酰胺由一系列二氯酯或酰胺和各种糖醛合成。该过程以总的立体选择性和高收率进行。提出了一种基于顺序铬促进的醛醇型反应和完全立体选择性β-消除反应的机理来解释这些结果。

  DOI：

  10.1021/jo200548g

文献信息

• Wittig-Type Olefination Catalyzed by PEG-telluride
  作者：Zheng-Zheng Huang、Song Ye、Wei Xia、Yi-Hua Yu、Yong Tang

  DOI：10.1021/jo025586h

  日期：2002.5.1

  Soluble poly(ethylene glycol) (PEG)-supported telluride 2 was designed and synthesized for catalytic Wittig-type reactions. It was found that the catalytic loading could be reduced from 20 to 2 mol % by the introduction of PEG (even to 0.5 mol % when some telluride salts were used as the catalyst). Under the catalytic reaction conditions, a wide variety of aldehydes with different structures could

  设计并合成了可溶的聚乙二醇（PEG）负载的碲化物2，用于催化Wittig型反应。发现通过引入PEG可以将催化负载量从20mol％降低至2mol％（当使用一些碲化物盐作为催化剂时甚至可以降低至0.5mol％）。在催化反应条件下，具有不同结构的多种醛可以与溴乙酸酯反应，以高收率和优异的E-立体选择性提供β-取代的或α，β-二取代的不饱和酯。通过使用亚硫酸氢钠代替亚磷酸三苯酯的改进方法代表了非常简单的产物分离程序。公开了PEG在促进叶立德形成和稳定催化物质中的作用。还研究了该机制。
• A short stereoselective synthesis of the protected uracil 3′-epi-polyoxin C
  作者：Jozef Gonda、Miroslava Martinková、Andrea Baur

  DOI：10.1016/j.tetasy.2011.02.004

  日期：2011.1

  A short synthetic approach to the protected uracil 3′-epi-polyoxin C 20 has been developed. The stereoselective [3,3]-sigmatropic rearrangement of the corresponding 7-thiocyanato-α-d-xylo-hept-5-enfuranose 6 was employed as the key step to construct the C-5 stereocentre in 5-isothiocyanato-α-d-gluco-hept-6-enfuranose 8 and the formal synthesis of uracil 3′-epi-polyoxin C has been accomplished for the

  已经开发了一种用于保护的尿嘧啶3'-表-多聚氧还蛋白C 20的短合成方法。相应的7-硫氰酸根-α-d-二甲苯基-庚5-呋喃糖6的立体选择性[3,3]-σ重排被用作构建5-异硫氰酸根-α-d中C-5立体中心的关键步骤-葡萄糖-庚基-6-呋喃糖8和尿嘧啶3'-表-多聚毒素C的正式合成是首次完成。这种合成提供了一种简便的方法来制备多克级的水垢，因此对于研究多毒素的结构与活性之间的关系以及寻找更有效和有效的抗候选人剂很有用。
• Synthesis of five and six membered aminocyclitols: stereoselective Michael and Henry reaction approach with d-glucose derived α,β-unsaturated ester
  作者：Chaitali Chakraborty、Vinod P. Vyavahare、Vedavati G. Puranik、Dilip D. Dhavale

  DOI：10.1016/j.tet.2008.07.049

  日期：2008.9

  The stereoselective intermolecular Michael addition of nitromethane to d-glucose derived α,β-unsaturated ester 7 afforded l-ido-configurated nitroester 8 as the only product that on reduction of the ester functionality, cleavage of 1,2-acetonide and the intramolecular Henry reaction afforded exclusively muco-nitroinositol 9. While reduction of the ester functionality in 8, deprotection of 1,2-acetonide

  将硝基甲烷立体选择性地分子间迈克尔加成到d-葡萄糖衍生的α，β-不饱和酯7中，得到了l-氨基构型的硝酸酯8，这是唯一的酯官能度降低，1,2-丙酮化物裂解和分子内亨利分解的产物。反应，得到只粘膜-nitroinositol 9。虽然减少了8中的酯官能度，1,2-丙酮化物的脱保护，NaIO 4的氧化裂解和分子内的亨利反应提供了硝基环戊醇13。硝基环醇9和13分别转化为羟乙基取代的氨基环己糖醇5和氨基环戊糖醇6。
• [1,3]-Dipolar intramolecular nitrone olefin cycloaddition reaction of a sugar-derived α,β-unsaturated ester: a new diastereo- and regioselective synthesis of an aminocyclopentitol
  作者：Santosh M Jachak、Navnath P Karche、Dilip D Dhavale

  DOI：10.1016/s0040-4039(01)00877-2

  日期：2001.7

  The reaction of hemiacetal 2a, from the sugar derived α,β-unsaturated ester 1a, with N-benzylhydroxylamine hydrochloride in situ generates an N-benzylnitrone as a 1,3-dipole, which spontaneously undergoes diastereo- and regioselective intramolecular nitrone olefin cycloaddition to afford a hydroxy functionalised 4-exo-ethoxycarbonyl-3-oxa-2-azabicyclo[3.3.0]octane system, a precursor to a hitherto

  由糖衍生的α，β-不饱和酯1a产生的半缩醛2a与N-苄基羟胺盐酸盐原位反应，生成N-苄基硝酮为1,3-偶极子，它自发经历非对映和区域选择性的分子内硝酮烯烃环加成反应得到羟基官能化的4-外-乙氧基羰基-3-氧杂-2-氮杂双环[3.3.0]辛烷体系，这是迄今未知的氨基环戊醇衍生物的前体。
• Synthesis of a new amino acid-antibiotic, oxetin and its three stereoisomers.
  作者：YUTAKA KAWAHATA、SUGURU TAKATSUTO、NOBUO IKEKAWA、MASATSUNE MURATA、SATOSHI OMURA

  DOI：10.1248/cpb.34.3102

  日期：——

  Oxetin (1a), a unique antibiotic having an oxetane ring, and its three stereoisomers (1b, 1c, and 1d) were synthesized from the known aldehyde (6) by utilizing a highly regio- and stereoselective epoxide ring-opening reaction. The biological activities of these oxetin stereoisomers were compared.

  Oxetin（1a）是一种独特的含氧杂环的抗生素，其三种立体异构体（1b、1c和1d）是通过利用高度区域和立体选择性环氧化开环反应从已知的醛（6）合成的。对这些氧杂环立体异构体的生物活性进行了比较。