(1R,2S,3S,7aR)-1,2-dihydroxy-3-hydroxymethylhexahydro-1H-pyrrolizidine | 1256344-62-3

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡咯里西啶类
• 英文名称: (1R,2S,3S,7aR)-1,2-dihydroxy-3-hydroxymethylhexahydro-1H-pyrrolizidine
• 英文别名: (1S,2R,3R,7aS)-3-hydroxymethylhexahydro-1H-pyrrolizine-1,2-diol；7a-epi-(-)-hyacinthacine A₁；(1R,2S,3S,7aR)-1,2-dihydroxy-3-(hydroxymethyl)pyrrolizidine；(1R,2S,3S,7aR)-1,2-dihydroxy-3-(1-hydroxymethyl)hexahydro-1H-pyrrolizine；(1R,2S,3S,8R)-3-(hydroxymethyl)-2,3,5,6,7,8-hexahydro-1H-pyrrolizine-1,2-diol
• CAS: 1256344-62-3
• 化学式: C₈H₁₅NO₃
• 分子量: 173.212
• InChiKey: STFSMGASTIYWRS-CWKFCGSDSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  -0.7
• 重原子数：
  12
• 可旋转键数：
  1
• 环数：
  2.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  63.9
• 氢给体数：
  3
• 氢受体数：
  4

反应信息

• 作为产物：
  描述：

  tert-butyl (2R,3S,4S,5R,αR)-2-hydroxy-3-[N-but-3'-enyl-N-(α-methyl-p-methoxybenzyl)amino]-4,5-O-isopropylidenehept-6-enoate 在 Grubbs catalyst first generation 、 盐酸 、 sodium periodate 、 lithium aluminium tetrahydride 、 碘 、 碳酸氢钠 作用下， 以 四氢呋喃 、 甲醇 、 二氯甲烷 、 水 为溶剂， 反应 46.0h， 生成 (1R,2S,3S,7aR)-1,2-dihydroxy-3-hydroxymethylhexahydro-1H-pyrrolizidine
  参考文献：
  名称：

  Asymmetric Synthesis of Polyhydroxylated Pyrrolizidines via Transannular Iodoamination with Concomitant N-Debenzylation

  摘要：

  The doubly diastereoselective "matched" conjugate addition of lithium (R)-N-but-3-enyl-N-(alpha-methyl-p-methoxybenzyl)amide to tert-butyl (4S,5R,E)-4,5-O-isopropylidene-2,7-dienoate (derived from D-ribose in 3 steps) and in situ enolate oxidation with (-)-camphorsulfonyloxaziridine was followed by ring-closing metathesis with Grubbs 1 to give a hexahydroazocine scaffold. Subsequent treatment with I-2 resulted in transannular Iodoamination accompanied by loss of the alpha-methyl-p-methoxybenzyl group to give the corresponding pyrrolizidine scaffold as a single diastereoisomer upon direct crystallization from the crude reaction mixture. Further functional group manipulations enabled the preparation of (-)-7a-epi-hyacinthacine A1.

  DOI：

  10.1021/ol103090z

文献信息

• Polyhydroxylated pyrrolizidine alkaloids from transannular iodoaminations: application to the asymmetric syntheses of (−)-hyacinthacine A1, (−)-7a-epi-hyacinthacine A1, (−)-hyacinthacine A2, and (−)-1-epi-alexine
  作者：E. Anne Brock、Stephen G. Davies、James A. Lee、Paul M. Roberts、James E. Thomson

  DOI：10.1039/c3ob40205c

  日期：——

  N-substituent) were readily prepared via conjugate addition of lithium (R)-N-but-3-enyl-N-(α-methyl-p-methoxybenzyl)amide to either tert-butyl (4S,5R,E)-4,5-dihydroxy-4,5-O-isopropylidene-2,7-dienoate (derived from D-ribose) or tert-butyl (S,S,E)-4,5-dihydroxy-4,5-O-isopropylidene-2,7-dienoate (derived from L-tartaric acid) coupled with in situ enolate oxidation with (−)-camphorsulfonyloxaziridine, followed

  取代的1,2,3,4,7,8-六氢偶氮cine碱支架的跨环碘代胺化已发展成为一种多用途，非对映异构的途径，从而能够合成一系列吡咯并idine啶生物碱，如（-）-乙酰丁胺碱的合成所证明的那样A1，（ - ） - 7a-图外延-hyacinthacine A1，（ - ） - hyacinthacine A2，和（ - ） - 1-外延-alexine。必要的1,2,3,4,7,8-六氢偶氮cine碱（带有N -α-甲基-对甲氧基苄基或无N-取代基）可以通过共轭加成（R）-N-丁-3-烯基-N-（α-甲基-对甲氧基苄基）酰胺锂要么叔丁基（4小号，5 - [R ，ê）-4,5-二羟基-4,5- ö异亚丙基-2,7-二烯酸酯（衍生自D-核糖）或叔丁基（S，S，E）-4,5-二羟基-4,5- O-异亚丙基-2,7-二烯酸酯（衍生自L-酒石酸），再用（-）-樟脑磺酰基恶二丙啶原位烯醇氧化，然后用Grubbs
• Structure-Guided Minimalist Redesign of the L-Fuculose-1-Phosphate Aldolase Active Site: Expedient Synthesis of Novel Polyhydroxylated Pyrrolizidines and their Inhibitory Properties Against Glycosidases and Intestinal Disaccharidases
  作者：Xavier Garrabou、Livia Gómez、Jesús Joglar、Sergi Gil、Teodor Parella、Jordi Bujons、Pere Clapés

  DOI：10.1002/chem.201000714

  日期：2010.9.17

  L‐fuculose‐1‐phosphate aldolase from E. coli FucA was envisaged, to extend its tolerance towards bulky and conformationally restricted N‐Cbz‐amino aldehyde acceptor substrates (Cbz=benzyloxycarbonyl). Various mutants at the active site of the FucA wild type were obtained and screened with seven sterically demanding N‐Cbz‐amino aldehydes including N‐Cbz‐prolinal derivatives. FucA F131A showed an aldol activity of

  设想了对来自大肠杆菌FucA的L-岩藻糖-1-磷酸醛缩酶的最小活性位点重新设计，以扩展其对庞大且构象受限的N -Cbz-氨基醛受体底物（Cbz =苄氧基羰基）的耐受性。获得了FucA野生型活性位点的各种突变体，并用7种空间需求的N -Cbz-氨基醛（包括N -Cbz-脯氨酸衍生物）进行了筛选。FucA F131A显示具有（R）‐ N的醛醇活性为62μmolh -1  mg -1-Cbz-脯氨酸，而在FucA野生型中未观察到可检测的活性。对于其他底物，F131A突变体的羟醛酶活性比野生型FucA高4至25倍。关于反应的立体化学，（R）-氨基醛仅产生抗构型的羟醛加合物，而它们的S对应物给出反/顺非对映异构体的可变比例。有趣的是，F131A突变体对（R）-和（S）-N -Cbz-脯氨酸均具有高度立体选择性，仅产生抗和合成醛醇加合物分别。分子模型表明，这种改进的对大体积和刚性更大的底物（例如氮）的
• Nitro-polyols via Pyridine Promoted C═C Cleavage of 2-Nitroglycals. Application to the Synthesis of (−)-Hyacinthacine A1
  作者：Shengbiao Tang、De-Cai Xiong、Shende Jiang、Xin-Shan Ye

  DOI：10.1021/acs.orglett.5b03607

  日期：2016.2.5

  A mild and convenient transformation for the synthesis of nitro-polyols is described. The nitro-polyol derivatives were prepared either from 2-nitroglycals via a pyridine-promoted scission of the carbon–carbon double bond or from glycals via a sequential nitration–scission procedure. The generated nitro-polyols could undergo a stereoselective Michael addition reaction. The utility of the addition products

  描述了用于合成硝基多元醇的温和且方便的转化。硝基多元醇衍生物是由2-硝基糖类通过吡啶促进的碳-碳双键断裂或序贯硝化-断裂过程由糖类制备的。生成的硝基多元醇可能会发生立体选择性迈克尔加成反应。通过（-）-扁豆碱A1和7a- epi -（-）-扁豆碱A1的简明合成来举例说明添加产物的效用。
• Asymmetric Synthesis of Polyhydroxylated Pyrrolizidines via Transannular Iodoamination with Concomitant <i>N</i>-Debenzylation
  作者：E. Anne Brock、Stephen G. Davies、James A. Lee、Paul M. Roberts、James E. Thomson

  DOI：10.1021/ol103090z

  日期：2011.4.1

  The doubly diastereoselective "matched" conjugate addition of lithium (R)-N-but-3-enyl-N-(alpha-methyl-p-methoxybenzyl)amide to tert-butyl (4S,5R,E)-4,5-O-isopropylidene-2,7-dienoate (derived from D-ribose in 3 steps) and in situ enolate oxidation with (-)-camphorsulfonyloxaziridine was followed by ring-closing metathesis with Grubbs 1 to give a hexahydroazocine scaffold. Subsequent treatment with I-2 resulted in transannular Iodoamination accompanied by loss of the alpha-methyl-p-methoxybenzyl group to give the corresponding pyrrolizidine scaffold as a single diastereoisomer upon direct crystallization from the crude reaction mixture. Further functional group manipulations enabled the preparation of (-)-7a-epi-hyacinthacine A1.