(-)-6-deoxy-1,2:3,4-di-O-isopropylidene-α-D-galactopyranos-6-yl benzoate | 50720-98-4

• 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: (-)-6-deoxy-1,2:3,4-di-O-isopropylidene-α-D-galactopyranos-6-yl benzoate
• 英文别名: 6-O-benzoyl-1,2;3,4-di-O-isopropylidene-α-D-galactopyranose；((3aR,5R,5aS,8aS,8bR)-2,2,7,7-tetramethyltetrahydro-3aH-bis[1,3]dioxolo[4,5-b:4',5'-d]pyran-5-yl)methyl benzoate；[(1S,2R,6R,8R,9S)-4,4,11,11-tetramethyl-3,5,7,10,12-pentaoxatricyclo[7.3.0.02,6]dodecan-8-yl]methyl benzoate
• CAS: 50720-98-4
• 化学式: C₁₉H₂₄O₇
• 分子量: 364.395
• InChiKey: PVMUOTUDLIZEAN-RUCLQGLUSA-N

物化性质

• 沸点：
  443.8±40.0 °C(Predicted)
• 密度：
  1.174±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.2
• 重原子数：
  26
• 可旋转键数：
  4
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.63
• 拓扑面积：
  72.4
• 氢给体数：
  0
• 氢受体数：
  7

反应信息

• 作为反应物：
  描述：

  (-)-6-deoxy-1,2:3,4-di-O-isopropylidene-α-D-galactopyranos-6-yl benzoate 在 Candida cylindracea lipase 作用下， 反应 24.0h， 生成 双丙酮半乳糖
  参考文献：
  名称：

  Application of lipases in the removal of protective groups on glycerides and glycosides

  摘要：

  DOI：

  10.1016/s0040-4039(00)96264-6
• 作为产物：
  描述：

  (3aR,5R,5aS,8aS,8bR)-5-(Dibromo-phenyl-methoxymethyl)-2,2,7,7-tetramethyl-tetrahydro-bis[1,3]dioxolo[4,5-b;4',5'-d]pyran 在 水 作用下， 生成 (-)-6-deoxy-1,2:3,4-di-O-isopropylidene-α-D-galactopyranos-6-yl benzoate
  参考文献：
  名称：

  苄氧基的二溴化：苄基糖苷中的糖基溴化物

  摘要：

  用溴代三氯甲烷和紫外线将糖衍生物中的苄氧基溴化，可快速制得α-溴苄氧基糖。在进一步辐射下，由苄基糖醚形成α，α-二溴苄氧基衍生物，而由苄基呋喃糖苷和吡喃糖苷生产糖基溴化物。

  DOI：

  10.1016/s0040-4039(01)80784-x

文献信息

• Visible-Light Photocatalysis Employing Dye-Sensitized Semiconductor: Selective Aerobic Oxidation of Benzyl Ethers
  作者：Li Ren、Ming-Meng Yang、Chen-Ho Tung、Li-Zhu Wu、Huan Cong

  DOI：10.1021/acscatal.7b03029

  日期：2017.12.1

  The aerobic oxidation is an attractive approach toward environmentally benign synthesis of fine chemicals. In addition, dye-sensitized semiconductors are underdeveloped photocatalysts for selective organic synthesis. With the aid of catalytic eosin Y-sensitized titanium dioxide, we have developed efficient aerobic photooxidation of benzyl ethers to benzoates, featuring low cost, high atom economy,

  有氧氧化是一种在环境上良性合成精细化学品的有吸引力的方法。另外，染料敏化半导体是用于选择性有机合成的未开发的光催化剂。借助于催化曙红Y敏化的二氧化钛，我们开发了苄基醚有效的好氧光氧化为苯甲酸酯的方法，具有低成本，高原子经济性，广泛的底物范围和用户友好的设置的特点。此外，初步的机理研究表明，反应途径可能需要通过可分离的过氧化物中间体进行光诱导的基于自由基的两步过程。
• Conversion of amides to esters by the nickel-catalysed activation of amide C–N bonds
  作者：Liana Hie、Noah F. Fine Nathel、Tejas K. Shah、Emma L. Baker、Xin Hong、Yun-Fang Yang、Peng Liu、K. N. Houk、Neil K. Garg

  DOI：10.1038/nature14615

  日期：2015.8

  Although enzymes are able to cleave amide bonds in nature, it is difficult to selectively break the carbon–nitrogen bond of an amide using synthetic chemistry; now the activation and cleavage of these bonds using nickel catalysts is used to convert amides to esters. Although enzymes are able to cleave amide bonds in nature, it is difficult to selectively break the carbon–nitrogen bond of an amide using synthetic chemistry. In this paper the authors demonstrate that amide C–N bonds can be activated and cleaved using nickel catalysts. They used this methodology to convert amides to esters, which is a challenging and underdeveloped transformation. Amides are common functional groups that have been studied for more than a century1. They are the key building blocks of proteins and are present in a broad range of other natural and synthetic compounds. Amides are known to be poor electrophiles, which is typically attributed to the resonance stability of the amide bond1,2. Although amides can readily be cleaved by enzymes such as proteases3, it is difficult to selectively break the carbon–nitrogen bond of an amide using synthetic chemistry. Here we demonstrate that amide carbon–nitrogen bonds can be activated and cleaved using nickel catalysts. We use this methodology to convert amides to esters, which is a challenging and underdeveloped transformation. The reaction methodology proceeds under exceptionally mild reaction conditions, and avoids the use of a large excess of an alcohol nucleophile. Density functional theory calculations provide insight into the thermodynamics and catalytic cycle of the amide-to-ester transformation. Our results provide a way to harness amide functional groups as synthetic building blocks and are expected to lead to the further use of amides in the construction of carbon–heteroatom or carbon–carbon bonds using non-precious-metal catalysis.

  尽管酶能够在自然界中断裂酰胺键，但利用合成化学选择性地打破酰胺的碳—氮键却很困难；现在，使用镍催化剂激活和断裂这些键被用于将酰胺转化为酯。本文作者证明，酰胺C—N键可以使用镍催化剂激活和断裂。他们利用这种方法将酰胺转化为酯，这是一种具有挑战性且发展不足的转化。酰胺是一类常见的官能团，一个多世纪以来一直被研究。它们是蛋白质的关键构建模块，存在于广泛的天然和合成化合物中。酰胺被认为是一种差的亲电试剂，这通常归因于酰胺键的共振稳定性。尽管酶如蛋白酶可以轻易地断裂酰胺，但利用合成化学选择性地打破酰胺的碳—氮键却很困难。在这里，我们证明酰胺碳—氮键可以使用镍催化剂激活和断裂。我们利用这种方法将酰胺转化为酯，这是一种具有挑战性且发展不足的转化。反应方法在极其温和的反应条件下进行，并避免了使用大量过量的醇亲核试剂。密度泛函理论计算为酰胺到酯转化的热力学和催化循环提供了见解。我们的结果为利用酰胺官能团作为合成构建块提供了一种方法，并有望进一步在非贵金属催化的碳—杂原子或碳—碳键构建中使用酰胺。
• Pd-Catalyzed <i>para</i>-selective C–H difluoromethylation of aromatic carbonyls
  作者：Yang-Jie Mao、Bing-Xin Wang、Qiu-Zi Wu、Kun Zhou、Shao-Jie Lou、Dan-Qian Xu

  DOI：10.1039/c8cc09129c

  日期：——

  highly para-selective C–H difluoromethylation of electron-deficient aromatic carbonyls was developed. Diverse substituted aromatic ketones and benzoates were selectively difluoromethylated at the remote para-site of carbonyl groups in moderate to good yields. Moreover, the difuoromethylation was also compatible with several complex bioactive molecules.

  开发了一种新型的钯催化的缺电子芳族羰基的高度对位选择性CH H二氟甲基化反应。在中度到良好的收率下，在羰基的远端对位上，选择性取代了各种取代的芳族酮和苯甲酸酯。此外，二氟甲基化还与几种复杂的生物活性分子相容。
• Acylation of carbohydrates over Al2O3: preparation of partially and fully acylated carbohydrate derivatives and acetylated glycosyl chlorides
  作者：Pallavi Tiwari、Anup Kumar Misra

  DOI：10.1016/j.carres.2005.11.035

  日期：2006.2

  protocol does not require the addition of any base or activator. This methodology has been further extended to the selective acylation of carbohydrate diols and the one-pot preparation of acetylated glycosyl chlorides direct from free reducing sugars. The yields obtained in most of the cases are excellent.

  据报道，使用酰氯和固体支持剂Al2O3对碳水化合物衍生物进行选择性和全O酰化。该协议不需要添加任何碱或活化剂。该方法已经进一步扩展到碳水化合物二醇的选择性酰化和直接从游离还原糖直接制备一锅乙酰化糖基氯的方法。在大多数情况下所获得的产量是极好的。
• Electrochemical glycosylation in the presence of a catalytic chemical mediator
  作者：Ludovic Drouin、Richard G. Compton、Antony J. Fairbanks

  DOI：10.1002/poc.1388

  日期：2008.6

  Electrochemical glycosylation of thioglycoside donors proceeds efficiently in an undivided cell in the presence of a catalytic amount of the chemical mediator (4-bromophenyl) ammoniumyl hexachloroantimonate (BAHA). In comparison with electrochemical glycosylation alone, the use of a catalytic amount of BAHA greatly increases the rate of reaction, reduces the potential required and inhibits ester-protecting

  在催化量的化学介质（4-溴苯基）六氯锑酸铵（BAHA）的存在下，硫糖苷供体的电化学糖基化在未分裂的细胞中有效进行。与单独的电化学糖基化相比，催化量的BAHA的使用大大提高了反应速度，降低了所需的电势并抑制了酯保护基的迁移。版权所有©2008 John Wiley＆Sons，Ltd.