3,5-(R)-O-benzylidene-2-O-trifluoromethanesulfonyl-L-rhamnono-1,4-lactone | 322726-62-5

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 有机磺酸及其衍生物
• 英文名称: 3,5-(R)-O-benzylidene-2-O-trifluoromethanesulfonyl-L-rhamnono-1,4-lactone
• 英文别名: (R)-3,5-O-benzylidene-2-O-trifluoromethanesulfonyl-L-rhamnono-1,4-lactone；3,5-O-benzylidene-2-O-trifluoromethanesulfonyl-L-rhamnono-1,4-lactone；[(2R,4S,4aS,7R,7aR)-4-methyl-6-oxo-2-phenyl-4,4a,7,7a-tetrahydrofuro[3,2-d][1,3]dioxin-7-yl] trifluoromethanesulfonate
• CAS: 322726-62-5
• 化学式: C₁₄H₁₃F₃O₇S
• 分子量: 382.314
• InChiKey: DGLQTBRPYIBXEN-RHBUKMAISA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.3
• 重原子数：
  25
• 可旋转键数：
  3
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  96.5
• 氢给体数：
  0
• 氢受体数：
  10

反应信息

• 作为反应物：
  描述：

  3,5-(R)-O-benzylidene-2-O-trifluoromethanesulfonyl-L-rhamnono-1,4-lactone 在 吡啶 、 甲醇 、 氧化汞红 、 potassium carbonate 、 乙酰氯 作用下， 以 四氢呋喃 、 丁酮 为溶剂， 反应 4.3h， 生成 methyl 2,4-anhydro-L-rhamnonate
  参考文献：
  名称：

  Two epimerisations in the formation of oxetanes from l-rhamnose: towards oxetane-containing peptidomimetics

  摘要：

  The methyl group in (R)-3,5-O-benzylidene-L-rhamnono-1,4-lactone 2, prepared from L-rhamnose 1 in 41% yield without need for chromatography, is axial and provides a good example of Mills' rule that the 'O-inside' conformations are, in general, more stable than alternative 'H-inside' conformations. The lactone 2 may be converted in two steps in an overall 57% yield to the rhamnono-oxetane 3, which should be useful in generating oxetane dipeptide isosteres and oxetane beta -amino acids and in determining the value of the oxetane ring in inducing secondary structure in small peptidomimetics. Methyl 2,4-anhydro-(S)-3,5-O-benzylidene-L-rhamnonate 11, in which both the phenyl and methyl groups are equatorial, is slightly more thermodynamically stable than 3, providing a rare exception to Mills' rule. X-ray crystal structures of 2 and 11 are reported. (C) 2000 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0957-4166(00)00360-8
• 作为产物：
  描述：

  L-rhamnopyranose 在 吡啶 、 水 、 溴 、 barium carbonate 作用下， 以 四氢呋喃 为溶剂， 反应 18.4h， 生成 3,5-(R)-O-benzylidene-2-O-trifluoromethanesulfonyl-L-rhamnono-1,4-lactone
  参考文献：
  名称：

  Two epimerisations in the formation of oxetanes from l-rhamnose: towards oxetane-containing peptidomimetics

  摘要：

  The methyl group in (R)-3,5-O-benzylidene-L-rhamnono-1,4-lactone 2, prepared from L-rhamnose 1 in 41% yield without need for chromatography, is axial and provides a good example of Mills' rule that the 'O-inside' conformations are, in general, more stable than alternative 'H-inside' conformations. The lactone 2 may be converted in two steps in an overall 57% yield to the rhamnono-oxetane 3, which should be useful in generating oxetane dipeptide isosteres and oxetane beta -amino acids and in determining the value of the oxetane ring in inducing secondary structure in small peptidomimetics. Methyl 2,4-anhydro-(S)-3,5-O-benzylidene-L-rhamnonate 11, in which both the phenyl and methyl groups are equatorial, is slightly more thermodynamically stable than 3, providing a rare exception to Mills' rule. X-ray crystal structures of 2 and 11 are reported. (C) 2000 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0957-4166(00)00360-8

文献信息

• 6-Deoxyhexoses from<scp>l</scp>-Rhamnose in the Search for Inducers of the Rhamnose Operon: Synergy of Chemistry and Biotechnology
  作者：Zilei Liu、Akihide Yoshihara、Ciarán Kelly、John T. Heap、Mikkel H. S. Marqvorsen、Sarah F. Jenkinson、Mark R. Wormald、José M. Otero、Amalia Estévez、Atsushi Kato、George W. J. Fleet、Ramón J. Estévez、Ken Izumori

  DOI：10.1002/chem.201602482

  日期：2016.8.22

  In the search for alternative non‐metabolizable inducers in the l‐rhamnose promoter system, the synthesis of fifteen 6‐deoxyhexoses from l‐rhamnose demonstrates the value of synergy between biotechnology and chemistry. The readily available 2,3‐acetonide of rhamnonolactone allows inversion of configuration at C4 and/or C5 of rhamnose to give 6‐deoxy‐d‐allose, 6‐deoxy‐d‐gulose and 6‐deoxy‐l‐talose. Highly

  在寻求在替代方案中不可代谢的诱导升鼠李糖启动子系统，十五6-脱氧己糖从合成升鼠李糖演示生物技术和化学之间的协同作用的值。rhamnonolactone的容易获得的2,3-丙酮允许构型的反转在C4和/或鼠李糖的C5，得到6-脱氧d -allose，6-脱氧d -gulose和6-脱氧升-talose。高度结晶的3,5-亚苄基rhamnonolactone可以轻松访问升-quinovose（6-脱氧升葡萄糖），升带有C2叠氮基，氨基和乙酰氨基取代基的寡糖和鼠李糖类似物。鼠李的亲电氟化作用产生了2-脱氧-2-氟-1-鼠李糖和2-脱氧-2-氟-1-鼠李糖的混合物。生物技术使人们能够获得6-脱氧-l-果糖和1-脱氧-l-果糖。
• Hanessian-Hullar reaction in the synthesis of highly substituted trans-3,4-dihydroxypyrrolidines: Rhamnulose iminosugar mimics inhibit α-glucosidase
  作者：Zilei Liu、Akihide Yoshihara、Sarah F. Jenkinson、Mark R. Wormald、Ciarán Kelly、John T. Heap、Mikkel H.S. Marqvorsen、Ramón J. Estévez、George W.J. Fleet、Shinpei Nakagawa、Ken Izumori、Robert J. Nash、Atsushi Kato

  DOI：10.1016/j.tet.2019.130758

  日期：2020.1

  4-dihydroxypyrrolidines is introduction of bromide by stereospecific and regiospecific Hanessian-Hullar reactions; benzylidene lactones of l-rhamnonolactone and 6-deoxy-l-gulonolactone allow introduction of N at C2 with inversion or retention of configuration. Initially a protecting group, the benzylidene acetal then provides a bromide at C5 to allow formation of the pyrrolidine ring. With silyl protecting

  合成高度取代的反式-3,4-二羟基吡咯烷酮的关键步骤是通过立体特异性和区域特异性Hanessian-Hullar反应引入溴化物。1-鼠李糖内酯和6-脱氧-1-古洛糖内酯的亚苄基内酯允许在C 2处引入N而具有构型的反转或保留。最初是保护基，亚苄基乙缩醛然后在C5处提供溴化物，以允许形成吡咯烷环。带有甲硅烷基保护基团时，溴在C5处以构型反转的方式引入，而苯甲酰基保护基团则提供保留和反转的混合物，表明相邻基团参与了Hanessian-Hullar反应。四种立体异构的吡咯烷-α-和β- 1的亚氨基糖模拟物-rhamnulose和α-和β-6脱氧d制备-sorbose。仅α- 1-鼠李糖糖模拟物显示出对鼠李糖苷酶的中等抑制作用，但是一些是α-葡萄糖苷酶的良好抑制剂。没有一种抑制鼠李糖异构酶，并且作为鼠李糖分解代谢操纵子在大肠杆菌中的合成诱导剂效果很小。
• Oxetane cis- and trans-β-amino-acid scaffolds from l-rhamnose by efficient SN2 reactions in oxetane rings; pseudoenantiomeric analogues of the antibiotic oxetin
  作者：Stephen W. Johnson、Sarah F. Jenkinson (née Barker)、Donald Angus、John H. Jones、George W.J. Fleet、Claude Taillefumier

  DOI：10.1016/j.tetasy.2004.07.032

  日期：2004.9

  An efficient multigram ring contraction of a 1,4-lactone 2-O-triflate derived from L-rhamnose-with retention of configuration in the ring closure-is the key step in the preparation of a series of oxetanes, which are pseudoenantiomeric analogues of the naturally occurring antibiotic oxetin, an oxetane cis-beta-amino acid. Subsequent nucleophilic displacements of the corresponding triflates by azide proceed in consistently excellent yields, without any elimination, to provide syntheses of scaffolds for analogues of the antibiotic. (C) 2004 Elsevier Ltd. All rights reserved.
• cis- and trans-3-Azido-oxetane-2-carboxylate scaffolds: hexamers of oxetane cis-β-amino acids
  作者：Sarah F Barker、Donald Angus、Claude Taillefumier、Michael R Probert、David J Watkin、Mark P Watterson、Timothy D.W Claridge、Natasha L Hungerford、George W.J Fleet

  DOI：10.1016/s0040-4039(01)00660-8

  日期：2001.6

  Efficient synthesis of both cis- and trans-3-azido-oxktane-2-carboxylates relies upon efficient nucleophilic displacements of 3-O-triflates of oxetanes by trifluoroacetate and azide. Such structures are scaffolds for incorporation of oxetane-beta-amino acids into oligomers; the synthesis of a series of protected beta-hexapeptides and the X-ray crystal structure of methyl 2,4-anhydro-6-deoxy-5-O-benzyl-L-altronate are reported. (C) 2001 Elsevier Science Ltd. AII rights reserved.
• Two epimerisations in the formation of oxetanes from l-rhamnose: towards oxetane-containing peptidomimetics
  作者：Stephen W Johnson、Donald Angus、Claude Taillefumier、John H Jones、David J Watkin、Emma Floyd、J.Grant Buchanan、George W.J Fleet

  DOI：10.1016/s0957-4166(00)00360-8

  日期：2000.10

  The methyl group in (R)-3,5-O-benzylidene-L-rhamnono-1,4-lactone 2, prepared from L-rhamnose 1 in 41% yield without need for chromatography, is axial and provides a good example of Mills' rule that the 'O-inside' conformations are, in general, more stable than alternative 'H-inside' conformations. The lactone 2 may be converted in two steps in an overall 57% yield to the rhamnono-oxetane 3, which should be useful in generating oxetane dipeptide isosteres and oxetane beta -amino acids and in determining the value of the oxetane ring in inducing secondary structure in small peptidomimetics. Methyl 2,4-anhydro-(S)-3,5-O-benzylidene-L-rhamnonate 11, in which both the phenyl and methyl groups are equatorial, is slightly more thermodynamically stable than 3, providing a rare exception to Mills' rule. X-ray crystal structures of 2 and 11 are reported. (C) 2000 Elsevier Science Ltd. All rights reserved.