3-O-tert-butyldimethylsilyl-L-rhamnal | 101856-96-6

• 分子结构分类: 有机化合物 - 有机金属化合物 - 有机类金属化合物
• 英文名称: 3-O-tert-butyldimethylsilyl-L-rhamnal
• 英文别名: 1,5-anhydro-3-O-[tert-butyl(dimethyl)silyl]-2,6-dideoxy-L-arabino-hex-1-enitol；(2S,3S,4S)-4-[tert-butyl(dimethyl)silyl]oxy-2-methyl-3,4-dihydro-2H-pyran-3-ol
• CAS: 101856-96-6
• 化学式: C₁₂H₂₄O₃Si
• 分子量: 244.406
• InChiKey: UJOBWNWTDACYCC-DCAQKATOSA-N

物化性质

• 沸点：
  287.1±40.0 °C(Predicted)
• 密度：
  0.98±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.67
• 重原子数：
  16
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.83
• 拓扑面积：
  38.7
• 氢给体数：
  1
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  3-O-tert-butyldimethylsilyl-L-rhamnal 在 四丁基氟化铵 、 双(三甲基硅烷基)氨基钾 作用下， 以 四氢呋喃 、 N,N-二甲基甲酰胺 为溶剂， 反应 0.25h， 生成 4-O-苄基-L-鼠李醛
  参考文献：
  名称：

  正交保护的6-脱氧葡萄糖糖基的模块化连续流合成。

  摘要：

  描述了一种有效的，模块化的连续流动方法，该方法旨在获得两个正交保护的糖，并为几种常见的保护基的流动反应条件的发展做出了贡献，其中包括苄基，萘基甲基和叔丁基二甲基甲硅烷基醚的添加。该方法仅在21-37分钟的流动时间内即可以57-74％的总收率提供所需的目标化合物。此外，与分批条件不同，该流动过程避免了需要主动冷却以防止有害的放热的需要，并且需要更短的反应时间。

  DOI：

  10.1039/d0ob00522c
• 作为产物：
  描述：

  2,3,4-tri-O-acetyl-L-rhamnopyranosyl bromide 在 甲醇 、 4-二甲氨基吡啶 、 sodium methylate 、 三乙胺 、 锌 作用下， 以 aq. phosphate buffer 、 乙酸乙酯 、 N,N-二甲基甲酰胺 为溶剂， 反应 0.66h， 生成 3-O-tert-butyldimethylsilyl-L-rhamnal
  参考文献：
  名称：

  Automated, Multistep Continuous‐Flow Synthesis of 2,6‐Dideoxy and 3‐Amino‐2,3,6‐trideoxy Monosaccharide Building Blocks

  摘要：

  AbstractAn automated continuous flow system capable of producing protected deoxy‐sugar donors from commercial material is described. Four 2,6‐dideoxy and two 3‐amino‐2,3,6‐trideoxy sugars with orthogonal protecting groups were synthesized in 11–32 % overall yields in 74–131.5 minutes of total reaction time. Several of the reactions were able to be concatenated into a continuous process, avoiding the need for chromatographic purification of intermediates. The modular nature of the experimental setup allowed for reaction streams to be split into different lines for the parallel synthesis of multiple donors. Further, the continuous flow processes were fully automated and described through the design of an open‐source Python‐controlled automation platform.

  DOI：

  10.1002/anie.202109887

文献信息

• A 3,4-<i>trans</i>-Fused Cyclic Protecting Group Facilitates α-Selective Catalytic Synthesis of 2-Deoxyglycosides
  作者：Edward I. Balmond、David Benito-Alifonso、Diane M. Coe、Roger W. Alder、Eoghan M. McGarrigle、M. Carmen Galan

  DOI：10.1002/anie.201403543

  日期：2014.7.28

  disaccharides or glycoconjugates with high α‐selectivity and yields (77–97 %) using a trans‐fused cyclic 3,4‐O‐disiloxane protecting group and TsOH⋅H2O (1 mol %) as a catalyst. Control of the anomeric selectivity arises from conformational locking of the intermediate oxacarbenium cation. Glucals outperform rhamnals because the C6 side‐chain conformation augments the selectivity.

  已经开发出一种实用的方法，使用反式稠合环状 3,4-O-二硅氧烷保护基团和 TsOH⋅H 2 O ，将葡糖和鼠李糖转化为具有高α-选择性和产率（77-97%）的二糖或糖缀合物（ 1 mol%) 作为催化剂。异头选择性的控制来自中间氧杂碳鎓阳离子的构象锁定。Glucals 优于鼠李糖醇，因为 C6 侧链构象增强了选择性。
• Reagent-Controlled Synthesis of the Branched Trisaccharide Fragment of the Antibiotic Saccharomicin B
  作者：Sameh E. Soliman、Clay S. Bennett

  DOI：10.1021/acs.orglett.8b01355

  日期：2018.6.1

  A concise synthesis of a branched trisaccharide, α-l-Dig-(1 → 3)-[α-l-Eva-(1 → 4)]-β-d-Fuc, corresponding to saccharomicin B, has been developed via reagent-controlled α-selective glycosylations. Starting from the d-fucose acceptor, l-epi-vancosamine was selectively installed using 2,3-bis(2,3,4-trimethoxyphenyl)cyclopropene-1-thione/oxalyl bromide mediated dehydrative glycosylation. Following deprotection

  通过试剂开发了一种精简的支链三糖α- 1- Dig-（1→3）-[α- 1- Eva-（1→4）]-β- d- Fuc的合成方法-控制的α-选择性糖基化。从d-岩藻糖受体开始，使用2，3-双（2,3,4-三甲氧基苯基）环丙烯-1-硫酮/草酰溴介导的脱水糖基化选择性地安装1 - epi- vancosamine。脱保护后，使用AgPF 6安装了l -digitoxose/ TTBP硫醚活化方法生产三糖，为单个α-端基异构体。这种高度功能化的三糖可以潜在地充当抗生素糖精B的全合成的供体和受体。
• Modular continuous flow synthesis of orthogonally protected 6-deoxy glucose glycals
  作者：Subbarao Yalamanchili、Tu-Anh V. Nguyen、Nicola L. B. Pohl、Clay S. Bennett

  DOI：10.1039/d0ob00522c

  日期：——

  An efficient, modular continuous flow process towards accessing two orthogonally protected glycals is described with the development of reaction conditions for several common protecting group additions in flow, including the addition of benzyl, naphthylmethyl and tert-butyldimethylsilyl ethers. The process affords the desired target compounds in 57-74% overall yield in just 21-37 minutes of flow time

  描述了一种有效的，模块化的连续流动方法，该方法旨在获得两个正交保护的糖，并为几种常见的保护基的流动反应条件的发展做出了贡献，其中包括苄基，萘基甲基和叔丁基二甲基甲硅烷基醚的添加。该方法仅在21-37分钟的流动时间内即可以57-74％的总收率提供所需的目标化合物。此外，与分批条件不同，该流动过程避免了需要主动冷却以防止有害的放热的需要，并且需要更短的反应时间。
• Simple oxidation of 3-O-silylated glycals: application in deblocking 3-O-protected glycals
  作者：Andreas Kirschning、Ulrike Hary、Claus Plumeier、Monika Ries、Lars Rose

  DOI：10.1039/a807479h

  日期：——

  A high yielding allylic oxidation of 3-O-silylated glycals 5–10 with the reagent system PhI(OAc)2–TMSN3 is presented. The iodine(III) species generated under these conditions is a lot more effective for generating carbohydrate-derived 3-trialkylsiloxy-2,3-dihydro-4H-pyran-4-ones 11–15 than is [hydroxy(tosyloxy)iodo]benzene, the Koser reagent. Even disaccharide 9 containing the oxidation-labile phenylseleno group is smoothly oxidized to the corresponding enone 15. The hypervalent azido iodine reagent is complementary to the Koser reagent, because 3-O-benzylated or -acylated glycals cannot be oxidized. When the iodine(III)-mediated oxidation of 3-O-silylated or -benzylated glycals is followed by a reduction step, the formal 3-O-deblocking of glycals is achieved. In particular, the Luche reduction of enones obtained from the oxidation of lyxo-configured glycals 24 and 26 is highly selective and exclusively affords the corresponding lyxo-configured glycals 28 and 30. In some cases, these products can be transformed under Mitsunobu conditions into glycals with inverted configuration at C-3 in moderate yield.

  提出了一种高产率的3-O-硅烷化糖醇5–10的烯丙氧化反应，使用的试剂系统为PhI(OAc)2–TMSN3。在这些条件下生成的碘(III)物种相比于Koser试剂[羟基(托芳基羟基)碘]苯，更有效地生成以碳水化合物为基础的3-三烷基硅氧基-2,3-二氢-4H-吡喃-4-酮11–15。即使是含有易氧化的苯基硒基的二糖9，也能平稳地氧化成相应的烯酮15。超价的叠氮碘试剂与Koser试剂互补，因为3-O-苄基化或-酰基化的糖醇无法被氧化。当3-O-硅烷化或-苄基化的糖醇进行碘(III)介导的氧化后再进行还原步骤时，可以实现糖醇的形式性3-O-去堵功能。特别是，从lyxo构型的糖醇24和26氧化得到的烯酮进行Luche还原反应时，选择性极高，专门生成相应的lyxo构型的糖醇28和30。在某些情况下，这些产物可以在Mitsunobu条件下转化为C-3配置反转的糖醇，且产率适中。
• Scope and Limitations of 2-Deoxy- and 2,6-Dideoxyglycosyl Bromides as Donors for the Synthesis of β-2-Deoxy- and β-2,6-Dideoxyglycosides
  作者：Miho Kaneko、Seth B. Herzon

  DOI：10.1021/ol501101f

  日期：2014.5.16

  It is shown that 2-deoxy- and 2,6-dideoxyglycosyl bromides can be prepared in high yield (72–94%) and engaged in glycosylation reactions with β:α selectivities ≥6:1. Yields of product are 44–90%. Fully armed 2-deoxyglycoside donors are viable, while 2,6-dideoxyglycosides require one electron-withdrawing substituent for high efficiency and β-selectivity. Equatorial C-3 ester protecting groups decrease

  结果表明，2-脱氧-和2,6-双脱氧糖基溴化物可以以高产率（72-94%）制备并参与糖基化反应，β:α选择性≥6:1。产品的产率为 44-90%。完全武装的 2-脱氧糖苷供体是可行的，而 2,6-双脱氧糖苷需要一个吸电子取代基以实现高效率和 β-选择性。赤道 C-3 酯保护基团会降低 β-选择性，并且带有轴向 C-3 取代基的供体不适合。该方法与含叠氮化物的供体和酸敏感官能团兼容。