4,6-di-O-acetyl-1,5-anhydro-2-deoxy-D-erythro-hex-1-en-3-ulose | 105544-73-8

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡喃
• 英文名称: 4,6-di-O-acetyl-1,5-anhydro-2-deoxy-D-erythro-hex-1-en-3-ulose
• 英文别名: [(2R,3R)-3-acetyloxy-4-oxo-2,3-dihydropyran-2-yl]methyl acetate
• CAS: 105544-73-8
• 化学式: C₁₀H₁₂O₆
• 分子量: 228.202
• InChiKey: YTUJZXRXIIWOGE-ZJUUUORDSA-N

物化性质

• 沸点：
  307.3±37.0 °C(Predicted)
• 密度：
  1.26±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  -0.1
• 重原子数：
  16
• 可旋转键数：
  5
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  78.9
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  4,6-di-O-acetyl-1,5-anhydro-2-deoxy-D-erythro-hex-1-en-3-ulose 在 palladium diacetate 吡啶 、 sodium tetrahydroborate 、 cerium(III) chloride 作用下， 以 乙腈 为溶剂， 反应 12.0h， 生成 4,5,7-tri-O-acetyl-2,6-anhydro-3-deoxy-D-manno-heptononitrile
  参考文献：
  名称：

  Palladium-catalyzed stereoselective C-glycosidation of unprotected enones derived from d-glucal with trimethylsilyl cyanide

  摘要：

  Acetylated and unprotected enones derived from D-glucal reacted with trimethylsilyl cyanide in the presence of a catalytic amount of a palladium compound in 1,4-addition fashion to afford the corresponding 3-keto-glycosyl cyanides in high yield and in high alpha-selectivity. (C) 2000 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0040-4039(00)00212-4
• 作为产物：
  描述：

  4,6-Di-O-acetyl-1,5-anhydro-3-O-(methoxymethyl)-2-deoxy-D-arabino-hex-1-enitol 在 3 A molecular sieve 、 羟基甲苯磺酰碘苯 作用下， 以 乙腈 为溶剂， 反应 1.25h， 以57%的产率得到4,6-di-O-acetyl-1,5-anhydro-2-deoxy-D-erythro-hex-1-en-3-ulose
  参考文献：
  名称：

  Oxidation of Fully Protected Glycals by Hypervalent Iodine Reagents

  摘要：

  A new application of organoiodine(III) is presented. Fully protected glycals are directly converted into 2,3-dihydro-4H-pyran-4-ones by [hydroxy(tosyloxy)iodo]benzene (PhI(OH)OTs, 1). The detailed study reveals that this conversion is independent of the relative stereochemistry as well as the nature of protection on the pyran ring. 3-O-Silyl groups are most smoothly converted into the keto group giving 2,3-dihydro-4H-pyran-4-ones in yields up to 74%. In contrast, 4,6-di-O-acetyl-3-deoxyglucal (19) affords the rearranged oxidation product 32. Both observations can be reconciled by the proposed mechanism.

  DOI：

  10.1021/jo00110a028
• 作为试剂：
  描述：

  4-戊烯-1-醇 、 4,6-di-O-acetyl-3-O-carbamoyl-D-glucal 在 dirhodium tetraacetate 、 亚碘酰苯 、 4,6-di-O-acetyl-1,5-anhydro-2-deoxy-D-erythro-hex-1-en-3-ulose 作用下， 以 二氯甲烷 为溶剂， 反应 1.75h， 以72%的产率得到4-pentenyl 2-amino-2-N-3-O-carbonyl-2-deoxy-4,6-di-O-acetyl-α-D-mannopyranoside
  参考文献：
  名称：

  Protecting Group and Solvent Control of Stereo- and Chemoselectivity in Glucal 3-Carbamate Amidoglycosylation

  摘要：

  In the Rh-2(OAC)(4)-catalyzed amidoglycosylation of glucal 3-carbamates, anomeric stereoselectivity and the extent of competing C3-H oxidation depend on the 40 and 60 protecting groups. Acyclic protection permits high alpha-anomer selectivity with further improvement in less polar solvents, while electron-withdrawing protecting groups limit C3-oxidized byproducts. Stereocontrol and bifurcation between alkene insertion and C3-H oxidation reflect an interplay of conformational, stereoelectronic, and inductive factors.

  DOI：

  10.1021/ol900126q

文献信息

• Michael-type additions in the synthesis of α-O- and -S-2-deoxyglycosides
  作者：Katja Michael、Horst Kessler

  DOI：10.1016/0040-4039(96)00616-8

  日期：1996.5

  O- and S-Nucleophiles including galactose, serine and cysteine derivatives undergo MICHAEL-type additions to hex-1-en-3-uloses to furnish stereoselectively the α-2-deoxy-ulosides. The keto function at C-3 can be reduced stereoelectively with NaBH4. Both configurations can be obtained depending on the presence or absence of CeCl3. Glycosylation takes place either base catalyzed with DBU (1,8-diazabicyclo[5

  包括半乳糖，丝氨酸和半胱氨酸衍生物在内的O-和S-Nucleophiles经过对hexa-1-en-3-ulose进行MICHAEL型加成，以立体选择性地提供α-2-deoxy-ulosides。用NaBH 4可以选择性地降低C-3处的酮基功能。取决于CeCl 3的存在与否，可以获得两种配置。糖基化发生在DBU（1,8-二氮杂双环[5.4.0]十一碳-7-烯）催化的碱或KCN / 18-crown-6或ZnI 2催化的酸中。
• Efficient Synthesis of Rare Sugar <scp>d</scp>-Allal via Reversal of Diastereoselection in the Reduction of Protected 1,5-Anhydrohex-1-en-3-uloses: Protecting Group Dependence of the Stereoselection
  作者：Takashi Fujiwara、Masahiko Hayashi

  DOI：10.1021/jo801596q

  日期：2008.11.21

  loses using the NaBH4CeCl3 x 7 H2O system. The crucial point of this synthesis is the nature of the protecting group. When bulky silyl group such as t-butyldiphenylsilyl was used as substrate, protected D-allal was obtained in >99% selectivity. In contrast, when acetylated enone was used, protected D-glucal was obtained exclusively. The addition of CeCl3 x 7 H2O was also found to influence selectivity

  D-alal是通过使用NaBH4 x 7 H2O系统还原大体积的甲硅烷基保护的1，5-脱水己基-1-en-3-uloses选择性获得的。该合成的关键点是保护基团的性质。当使用大体积的甲硅烷基如叔丁基二苯基甲硅烷基作为底物时，以> 99％的选择性获得了受保护的D-alal。相反，当使用乙酰化的烯酮时，仅获得保护的D-葡萄糖。还发现添加CeCl3 x 7 会影响选择性。
• Synthesis of the positron-emitting radiotracer [¹⁸F]-2-fluoro-2-deoxy-<scp>d</scp>-glucose from resin-bound perfluoroalkylsulfonates
  作者：Lynda J. Brown、Nianchun Ma、Denis R. Bouvet、Sue Champion、Alex M. Gibson、Yulai Hu、Alex Jackson、Imtiaz Khan、Nicolas Millot、Amy C. Topley、Harry Wadsworth、Duncan Wynn、Richard C. D. Brown

  DOI：10.1039/b816032e

  日期：——

  A new approach to the synthesis of 2-fluoro-2-deoxy-D-glucose (FDG, [19/18F]-3) is described, which employs supported perfluoroalkylsulfonate precursors 33–36, where the support consists of insoluble polystyrene resin beads. Treatment of these resins with [19F]fluoride ion afforded protected FDG [19F]-18 as the major product, and the identities of the main byproducts were determined. Acidic removal

  一种新的合成方法 2-氟-2-脱氧-D-葡萄糖（FDG，[ 19/ 18 F] - 3）进行说明，其采用支撑全氟烷前体33-36，其中该载体是由不溶性聚苯乙烯树脂珠。用[ 19 F]氟离子处理这些树脂，得到保护的FDG [ 19 F] -18作为主要产物，并确定了主要副产物的身份。从[ 19 F] -18酸去除乙缩醛保护基表明产生了[ 19 F] FDG。该方法已应用于显像剂的高效放射合成[ 18F] FDG，并显示出以良好的放射化学收率（平均73％，已校正衰变）产生放射化学示踪剂。
• Convenient Preparations of 2,3-Dihydro-4H-pyran-4-ones from D-Glucal Triacetate : Selective Oxidations of Alyllic Acetates and Allylic Silyl Ethers Using N-Bromosuccinimide
  作者：Anne Bouillot、Duc Do Khac、Marcel Fétizon、Frédéric Guir、Yvone Memoria

  DOI：10.1080/00397919308018600

  日期：1993.8

  Abstract N-Bromosuccinimide (1.1 eq) in the presence of potassium carbonate (2 eq) and a catalytic amount of dibenzoyl peroxide converts the allylic acetates and the allylic silyl ethers (O-TBDMS or O-SiEt3) of secondary allylic alcohols, derived from D-glucal 3a into corresponding dihydro γ-pyrones 2.

  摘要 N-溴代琥珀酰亚胺 (1.1 eq) 在碳酸钾 (2 eq) 和催化量的过氧化二苯甲酰存在下，转化了烯丙醇的烯丙基乙酸酯和烯丙基甲硅烷基醚 (O-TBDMS 或 O-SiEt3)，衍生自D-glucal 3a 转化为相应的二氢 γ-吡喃酮 2。
• Palladium‐Catalyzed Reaction of Aryl Iodides and Glycal Enones: Application in the Preparation of Dapagliflozin Analogues
  作者：Adesh Kumar Singh、Rapelly Venkatesh、Vimlesh Kumar Kanaujiya、Varsha Tiwari、Jeyakumar Kandasamy

  DOI：10.1002/ejoc.202200023

  日期：2022.9.6

  A wide range of aryl iodides bearing electron-donating and withdrawing groups underwent oxidative C-1 arylation with enones derived from glycals in the presence of Pd(OAc)2 and AgNO3 under ligand-free conditions. The developed methodology was successfully applied in the preparation of dapagliflozin analogues (SGLT-2 inhibitor).

  在无配体条件下，在 Pd(OAc) 2和 AgNO 3存在下，各种带有给电子基团和吸电子基团的芳基碘化物与衍生自糖醛的烯酮发生氧化C -1 芳基化。所开发的方法成功地应用于制备达格列净类似物（SGLT-2 抑制剂）。