(1R,2S,3R,4S,5R)-8-氮杂双环[3.2.1]辛烷-1,2,3,4-四醇 | 127414-85-1

• 分子结构分类: 有机化合物 - 生物碱及其衍生物 - 托烷生物碱
• 中文名称: (1R,2S,3R,4S,5R)-8-氮杂双环[3.2.1]辛烷-1,2,3,4-四醇
• 英文名称: calystegin B2
• 英文别名: calystegine B₂；Calystegine B2；(1R,2S,3R,4S,5R)-8-azabicyclo[3.2.1]octane-1,2,3,4-tetrol
• CAS: 127414-85-1
• 化学式: C₇H₁₃NO₄
• 分子量: 175.185
• InChiKey: FXFBVZOJVHCEDO-IBISWUOJSA-N

物化性质

• 沸点：
  341.0±42.0 °C(Predicted)
• 密度：
  1.722

计算性质

• 辛醇/水分配系数(LogP)：
  -2.4
• 重原子数：
  12
• 可旋转键数：
  0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  93
• 氢给体数：
  5
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  (1R,2S,3R,4S,5R)-8-氮杂双环[3.2.1]辛烷-1,2,3,4-四醇 、 乳糖 在 phosphate buffer 、 whole cells of R_. lactosa 作用下， 以 水 为溶剂， 反应 72.0h， 以10.1%的产率得到(1R,2S,3S,4S,5R)-4-[(2R,3R,4S,5R,6R)-3,4,5-trihydroxy-6-(hydroxymethyl)oxan-2-yl]oxy-8-azabicyclo[3.2.1]octane-1,2,3-triol
  参考文献：
  名称：

  Enzymatic synthesis of the glycosides of calystegines B1 and B2 and their glycosidase inhibitory activities

  摘要：

  Several glycosides of calystegines B-1 and B-2 were synthesized by use of rice a-glucosidase and the whole cells of Rhodotorula lactosa, and their glycosidase inhibitory activities were investigated. Incubation of a mixture of calystegine B-1 and maltose with rice cr-glucosidase gave 3-O-alpha-D-glucopyranosylcalystegine B-1 (2, 11.3%). An enzymatic beta-transglucosylation reaction of calystegines B-1 or B-2 with cellobiose using the whole cells of R. lactosa gave 3-O-beta-D-glucopyranosylcalystegine B-1 (1) (0.9%) or 4-O-beta-D-glucopyranosylcalystegine B-2 (3, 11.2%), respectively, while a similar beta-transgalactosylation of calystegine B-2 from lactose gave 4-O-beta-D-galactopyranosylcalystegine B-2 (4, 10.1%). The glycosylation of calystegines B-1 and B-2 markedly decreased or abolished their inhibition against beta-glucosidase, alpha- or beta-galactosidase. Compound 4 however retained more or less the potency of calystegine B-2 against trehalase. Interestingly, compound 1 was a noncompetitive inhibitor of rice alpha-glucosidase, with a K-1 value of 0.9 +/- 0.1 mu M. (C) 1997 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0008-6215(97)00227-9
• 作为产物：
  描述：

  methyl 6-deoxy-6-iodo-2,3,4-tri-O-benzyl-α-D-glucopyranoside 在 RuCl2(1,3-dimesityl-imidazolidin-2-yl)(PCy3)(=CHPh) 、 palladium dihydroxide 盐酸 、 三甲基氯硅烷 、 硼烷四氢呋喃络合物 、 氢气 、 potassium hydrogencarbonate 、 锌 作用下， 以 四氢呋喃 、 二氯甲烷 、 水 为溶剂， -40.0~40.0 ℃ 、101.33 kPa 条件下， 反应 54.86h， 生成 (1R,2S,3R,4S,5R)-8-氮杂双环[3.2.1]辛烷-1,2,3,4-四醇
  参考文献：
  名称：

  合成花萼碱生物碱的短途径。

  摘要：

  描述了一种用于合成对映纯的卡司他汀生物碱的有效策略。关键步骤是用锌介导的苄基保护的甲基6-碘-糖苷片段化，然后原位形成苄基亚胺，并与锌，镁或铟金属进行Barbier型烯丙基化。关键的烯丙基化中的立体化学是通过选择金属来控制的。如此形成的官能化的1,8-壬二烯通过闭环烯烃复分解反应转化为环庚烯。区域选择性氢硼化和氧化得到相应的环庚酮，将其去保护得到所需的金刚烷基酯。由此，分别从D-葡萄糖，D-半乳糖和D-甘露糖制备卡来斯汀B（2），B（3）和B（4）。

  DOI：

  10.1021/jo020645c

文献信息

• Synthesis of nortropane alkaloid calystegine B2 from methyl α-d-xylopyranoside
  作者：Emilie N. Underlin、Henrik H. Jensen

  DOI：10.1016/j.carres.2018.12.002

  日期：2019.1

  A new synthetic route for formation of a central cycloheptanone intermediate leading to the nortropane alkaloid calystegine B2 is described. The approach installs the desired ketone functionality directly in a ring-closing metathesis step. The target compound was prepared over 10 steps from commercially available methyl α-d-xylopyranoside.

  描述了形成中央环庚酮中间体的新合成途径，该中间体导致降冰片烷生物碱calystegine B2。该方法直接在闭环复分解步骤中安装所需的酮官能团。由市售的甲基α-d-吡喃吡喃糖苷经10个步骤制备目标化合物。
• General access to polyhydroxylated nortropane derivatives through hetero Diels–Alder cycloadditions. Part 3: Synthesis of natural (+)-calystegine B2
  作者：Thomas Faitg、Josette Soulié、Jean-Yves Lallemand、Louis Ricard

  DOI：10.1016/s0957-4166(99)00204-9

  日期：1999.6

  Cycloaddition of chiral nitroso derivatives with cyclohepta-1,3-diene gave one single stereoisomer with an excellent selectivity. The structures including absolute configurations have been assigned by spectroscopy and X-ray crystallography. These studies have been applied to the total synthesis of the naturally occurring calystegine B2.

  手性亚硝基衍生物与环庚-1,3-二烯的环加成反应产生了一种具有优异选择性的单一立体异构体。包括绝对构型在内的结构已通过光谱学和X射线晶体学确定。这些研究已经应用于天然存在的calystegine B 2的全合成。
• Concise synthesis of calystegines B₂ and B₃via intramolecular Nozaki–Hiyama–Kishi reaction
  作者：Hong-Yao Wang、Atsushi Kato、Kyoko Kinami、Yi-Xian Li、George W. J. Fleet、Chu-Yi Yu

  DOI：10.1039/c6ob00697c

  日期：——

  The key step in the concise syntheses of calystegine B2 and its C-2 epimer calystegine B3 was the construction of cycloheptanone 8via an intramolecular Nozaki–Hiyama–Kishi (NHK) reaction of 9, an aldehyde containing a Z-vinyl iodide. Vinyl iodide 9 was obtained by the Stork olefination of aldehyde 10, derived from carbohydrate starting materials. Calystegines B2 (3) and B3 (4) were synthesized from

  简洁地合成calystegine B 2及其C-2差向异构体calystegine B 3的关键步骤是通过分子内的Nozaki-Hiyama-Kishi（NHK）反应9（一种含有Z-乙烯基碘的醛）来构建环庚酮8。乙烯基碘化物9是通过醛10的斯托克烯化反应获得的，醛10是从碳水化合物原料中衍生出来的。由D-木糖和L合成Calystegines B 2（3）和B 3（4）。-阿拉伯糖衍生物分别经过11个步骤，具有优异的总收率（27％和19％）。
• Enantioselective syntheses of polyhydroxylated nortropane derivatives: Total synthesis of (+) and (−)-calystegine B2
  作者：François-Didier Boyer、Jean-Yves Lallemand

  DOI：10.1016/s0040-4020(01)89584-3

  日期：1994.1

  (+) and (−)-Calystegine B2 were prepared from D-Glucose via Ferrier reaction followed by regiospecific ring enlargement of a polysubstituted cyclohexanone and intramolecular cyclisation of 4-aminocycloheptanone.

  （+）和（-）-Calystegine B 2由D-葡萄糖经Ferrier反应，然后进行多取代的环己酮的区域特异性环扩大和4-氨基环庚酮的分子内环化来制备。
• Short syntheses of enantiopure calystegine B2, B3, and B4
  作者：Philip R. Skaanderup、Robert Madsen

  DOI：10.1039/b102353p

  日期：——

  Calystegine B2, B3, and B4 have been prepared in 5 steps from the benzyl protected methyl 6-iodoglycopyranosides of glucose, galactose and mannose, respectively, by using a zinc-mediated domino reaction followed by ring-closing olefin metathesis as the key steps.

  Calystegine B2、B3 和 B4 分别由葡萄糖、半乳糖和甘露糖的苄基保护的甲基 6-碘糖吡喃糖苷分 5 步制备，采用锌介导的多米诺骨牌反应，然后是闭环烯烃复分解作为关键步骤。