(1R,2R,3R,5R,7aR)-1,2-bis(benzyloxy)-3-(benzyloxymethyl)-5-methyl-hexahydro-1H-pyrrolizine | 1227867-85-7

• 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: (1R,2R,3R,5R,7aR)-1,2-bis(benzyloxy)-3-(benzyloxymethyl)-5-methyl-hexahydro-1H-pyrrolizine
• 英文别名: (3R,5R,6R,7R,7aR)-6,7-bis(benzyloxy)-5-(benzyloxymethyl)-3-methyl-hexahydro-1H-pyrrolizine；(1R,2R,3R,5R,8R)-5-methyl-1,2-bis(phenylmethoxy)-3-(phenylmethoxymethyl)-2,3,5,6,7,8-hexahydro-1H-pyrrolizine
• CAS: 1227867-85-7
• 化学式: C₃₀H₃₅NO₃
• 分子量: 457.613
• InChiKey: UCPXZQBNLJMDMD-XTBAWBFXSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.3
• 重原子数：
  34
• 可旋转键数：
  10
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.4
• 拓扑面积：
  30.9
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  (1R,2R,3R,5R,7aR)-1,2-bis(benzyloxy)-3-(benzyloxymethyl)-5-methyl-hexahydro-1H-pyrrolizine 在 盐酸 、 palladium 10% on activated carbon 、 氢气 作用下， 以 甲醇 、 水 为溶剂， 反应 96.0h， 以88%的产率得到(1R,2R,3R,5R,7aR)-1,2-dihydroxy-3-hydroxymethyl-5-methylpyrrolizidine
  参考文献：
  名称：

  A flexible approach for the asymmetric syntheses of hyacinthacines A2, A3 and structural confirmation of hyacinthacine A3

  摘要：

  一种简洁灵活的方法已被开发，用于不对称合成多羟基吡咯里啶生物碱海葱碱A2和A3，关键步骤是对O,O′-二苄基酒石酰亚胺（5）进行迭代还原烷基化。由于合成材料（2）和天然产品（海葱碱A3）在核磁共振（NMR）数据上的差异，合成海葱碱A3的结构存在歧义，通过综合的1D和2D-NMR研究以及对合成混合产物和天然海葱碱A3的1H和13C NMR光谱分析，消除了这一歧义。后者方法还确认了天然海葱碱A3的结构，并可能对其他羟基化生物碱的结构确认有用。

  DOI：

  10.1039/b926741g
• 作为产物：
  描述：

  (3S,4R,5R)-5-benzyloxymethyl-3,4-dibenzyloxy-1-(4-methoxybenzyl)-pyrrolidin-2-one 在 2,6-二叔丁基-4-甲基吡啶 、 ammonium cerium (IV) nitrate 、 三氟甲磺酸酐 、 palladium 10% on activated carbon 、 氢气 、 氧气 、 copper(l) chloride 、 palladium dichloride 作用下， 以 甲醇 、 二氯甲烷 、 水 、 N,N-二甲基甲酰胺 、 乙腈 为溶剂， -78.0~20.0 ℃ 、101.33 kPa 条件下， 反应 37.75h， 生成 (1R,2R,3R,5R,7aR)-1,2-bis(benzyloxy)-3-(benzyloxymethyl)-5-methyl-hexahydro-1H-pyrrolizine 、 (1R,2R,3R,5S,7aR)-1,2-bis(benzyloxy)-3-(benzyloxymethyl)-5-methyl-hexahydro-1H-pyrrolizine
  参考文献：
  名称：

  A concise and divergent approach to radicamine B and hyacinthacine A3 based on a step-economic transformation

  摘要：

  Based on our recently developed step-economic methodology of reductive alkylation of lactams/amides, we have developed a two-step synthesis of azasugar radicamine B (2a) and a four-step synthesis of azasugar hyacinthacine A(3) (5) from the common chiral building block 12. Hantzsch ester (HEH) was used as a milder hydride donor in the one-pot stereoselective reductive alkylation of lactam 12. The Wacker oxidation of fully substituted pyrrolidine derivative 2,5-trans-17 led to the synthesis of hyacinthacine A(3) (5). Compound 2,5-trans-17 could also serve as a plausible key intermediate for the synthesis of broussonetine sub-class of azasugars. (C) 2012 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tet.2012.01.085

文献信息

• A flexible approach for the asymmetric syntheses of hyacinthacines A2, A3 and structural confirmation of hyacinthacine A3
  作者：Wen-Jun Liu、Jian-Liang Ye、Pei-Qiang Huang

  DOI：10.1039/b926741g

  日期：——

  A concise and flexible approach for the asymmetric syntheses of polyhydroxylated pyrrolizidine alkaloids hyacinthacines A2 and A3 has been developed using iterative reductive alkylation of O,O′-dibenzyltartarimide (5) as key steps. The ambiguity about the structure of synthetic hyacinthacine A3 due to the differences in the NMR data of the synthetic material (2) and the natural product (hyacinthacine A3) was eliminated jointly by comprehensive 1D and 2D-NMR studies, and by analysis of the 1H and 13C NMR spectra of a mixed synthetic product and natural hyacinthacine A3. The latter method also allowed a confirmation of the structure of the natural hyacinthacine A3, and may be useful for structural confirmation of other hydroxylated alkaloids.

  一种简洁灵活的方法已被开发，用于不对称合成多羟基吡咯里啶生物碱海葱碱A2和A3，关键步骤是对O,O′-二苄基酒石酰亚胺（5）进行迭代还原烷基化。由于合成材料（2）和天然产品（海葱碱A3）在核磁共振（NMR）数据上的差异，合成海葱碱A3的结构存在歧义，通过综合的1D和2D-NMR研究以及对合成混合产物和天然海葱碱A3的1H和13C NMR光谱分析，消除了这一歧义。后者方法还确认了天然海葱碱A3的结构，并可能对其他羟基化生物碱的结构确认有用。
• A concise and divergent approach to radicamine B and hyacinthacine A3 based on a step-economic transformation
  作者：Jin-Cheng Liao、Kai-Jiong Xiao、Xiao Zheng、Pei-Qiang Huang

  DOI：10.1016/j.tet.2012.01.085

  日期：2012.7

  Based on our recently developed step-economic methodology of reductive alkylation of lactams/amides, we have developed a two-step synthesis of azasugar radicamine B (2a) and a four-step synthesis of azasugar hyacinthacine A(3) (5) from the common chiral building block 12. Hantzsch ester (HEH) was used as a milder hydride donor in the one-pot stereoselective reductive alkylation of lactam 12. The Wacker oxidation of fully substituted pyrrolidine derivative 2,5-trans-17 led to the synthesis of hyacinthacine A(3) (5). Compound 2,5-trans-17 could also serve as a plausible key intermediate for the synthesis of broussonetine sub-class of azasugars. (C) 2012 Elsevier Ltd. All rights reserved.