β-L-digitoxose | 138458-66-9

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: β-L-digitoxose
• 英文别名: (2S,4R,5R,6S)-6-methyloxane-2,4,5-triol
• CAS: 138458-66-9
• 化学式: C₆H₁₂O₄
• 分子量: 148.159
• InChiKey: FDWRIIDFYSUTDP-FSIIMWSLSA-N

物化性质

• 沸点：
  320.1±42.0 °C(Predicted)
• 密度：
  1.366±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  -1.1
• 重原子数：
  10
• 可旋转键数：
  0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  69.9
• 氢给体数：
  3
• 氢受体数：
  4

反应信息

• 作为产物：
  描述：

  rel-(5R,6S)-5,6-Dihydro-5-hydroxy-6-methyl-2H-pyran-2-one 在 吡啶 、 sodium hypochlorite 、 sodium tetrahydroborate 、 二苯基二硒醚 、 sodium acetate 、 sodium cyanoborohydride 、 溶剂黄146 作用下， 以 异丙醇 为溶剂， 反应 2.0h， 生成 β-L-digitoxose
  参考文献：
  名称：

  A divergent strategy for constructing a sugar library containing 2,6-dideoxy sugars and uncommon sugars with 4-substitution

  摘要：

  A practical strategy has been developed for delivering 2,6-dideoxy sugars and uncommon sugars with 4-substitution. This strategy employed Ferrier rearrangement reaction and BF3 center dot OEt2-induced peroxidation to construct key intermediates 2,3-unsaturated glycosides and alpha,beta-unsaturated lactones from peracetyl rhamnal. After further derivatization, four uncommon sugars with 4-substitution and eight uncommon sugar units with 3,4-disubstitution were successfully synthesized. (c) 2007 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tet.2007.07.019

文献信息

• De novo highly stereocontrolled synthesis of 2,6-dideoxy sugars by use of 2,6-anhydro-2-thio sugars
  作者：Kazunobu Toshima、Takehito Yoshida、Satsuki Mukaiyama、Kuniaki Tatsuta

  DOI：10.1016/0008-6215(91)89016-9

  日期：1991.12

  ribo -hexopyranose ( l -digitoxose) ( 33 ) have been stereospecifically synthesized through a highly stereoselective addition of a nucleophilic reagent to the C-3 carbonyl groups of methyl 2,6-anhydro-4- O -benzyl-2-thio-α- l - arabino -hexopyranosid-3-ulose ( 11 ) or methyl 2,6-anhydro-4- O -benzyl-2-thio-β- l - arabino -hexopyranosid-3-ulose ( 12 ) possessing 2,6-anhydro-2-thio structures. Anomers 11

  摘要代表性的2,6-二脱氧糖，1-cladinose（1），1-mycarose（2），1-oleandrose（3），1-olivose（4）及其所有C-3差向异构体2,6-双脱氧-3-C-甲基-3-O-甲基-1-阿拉伯糖-己糖（26），2,6-二脱氧-3-C-甲基-1-戊糖（1-寡果糖）（27），2通过立体定向合成了，6-二脱氧-3-O-甲基-1-核糖-己糖（l-cymarose）（32）和2,6-二脱氧-1-核糖-己糖（l-digitoxose）（33）。将亲核试剂高度立体选择性地加成到甲基2,6-脱水4-O-苄基-2-硫代-α-1-阿拉伯糖基-己吡喃糖苷-3-ulose（11）或甲基2的C-3羰基上具有2，6-脱水-2-硫代结构的1，6-脱水-4-O-苄基-2-硫代-β-1-阿拉伯糖-己吡喃糖苷-3-果糖（12）。异构体11和12均以立体控制的方式通过用Lewis处理常见的中间体甲基2
• 3-O-glycosyl 16-membered macrolide antibacterials and related derivatives
  申请人：Schering Corporation

  公开号：US04962146A1

  公开（公告）日：1990-10-09

  3-O-Glycosyl derivatives of 16-membered macrolides such as O-.alpha.-L-cladinosyl-(1.fwdarw.3)-12,13-dehydro-12,13-deoxorosaramicin, 2", 4",4'"-tri-O-acetyl-O-(4'-O-phenoxyacetyl-.alpha.-L-cladinosyl)-(1.fwdarw. 3)-desmyconsin and pharmaceutically acceptable acid addition salts thereof useful as antibacterials are disclosed.

  本发明涉及一种16元大环内酯类化合物的3-O-糖基衍生物，例如O-.alpha.-L-克拉地诺糖基-(1.fwdarw.3)-12,13-脱氢-12,13-脱氧罗沙霉素、2"、4"、4'"-三-O-乙酰基-O-(4'-O-苯氧基乙酰基)-.alpha.-L-克拉地诺糖基-(1.fwdarw.3)-去甲基链霉素以及其药学上可接受的酸盐加合物，作为抗菌剂。
• Nucleophilic Addition to 2,3-Disubstituted Butanal Derivatives and Their Application to Natural Product Synthesis
  作者：Hidekazu Horie、Hideaki Akaike、Keisuke Kato、Hiroyuki Akita

  DOI：10.1248/cpb.58.1411

  日期：——

  The reaction of 2,3-anti-2-tert-butyldimethylsiloxy-3-substituted butanal derivative [anti-B, (±)-10 and (±)-16] derived from trans-(2,3)-epoxy butanoate (1) with carbon nucleophiles [α-furyl anion, acetate anion, and indium (In)-assisted allyl anion] has been investigated to give selectively the anti-, anti-adduct D. This anti-stereoselection could be explained by the Felkin–Anh transition state model. Thus obtained anti-, anti-adducts (±)-17 and (±)-38 were formally converted to natural products, (±)-asperlin (2) and (±)-olivose (4), respectively. The major anti-, anti-adduct (±)-26 was converted to (±)-digitoxose (3), while the minor anti-, syn-adduct (±)-27 was also converted to (±)-olivose (4). The reaction of (±)-10 with tert-butyl acetate anion gave predominantly afforded the anti-, anti-adduct (±)-23, which was converted to (±)-1,5-dideoxyhexitol (25). Alternately, the reaction of 2,3-syn-2-tert-butyldimethylsiloxy-3-p-methoxyphenoxy butanal derivative [syn-B, (±)-14] derived from trans-(2,3)-epoxy butanoate (1) with carbon nucleophile (In-assisted allyl anion) afforded a ca. 1 : 1 mixture of the syn-, anti-adduct E [(±)-32 or (±)-34] and syn-, syn-adduct F [(±)-33 or (±)-35]. After separation of this mixture, (±)-34 and (±)-35 were separately converted to (±)-oliose (5) and (±)-boivinose (6), respectively.

  2,3-抗-2-叔丁基二甲基硅氧基-3-取代的丁醛衍生物[抗-B,(±)-10和(±)-16]衍生自反式-(2,3)-环氧丁酸酯的反应( 1）与碳亲核试剂[α-呋喃基阴离子、乙酸根阴离子和铟（In）辅助的烯丙基阴离子]进行了研究，以选择性地产生反加合物D。这种反立体选择可以通过Felkin- Anh 过渡状态模型。由此获得的抗-、抗加合物(±)-17和(±)-38分别正式转化为天然产物(±)-asperlin(2)和(±)-olivose(4)。主要的抗、抗加合物 (±)-26 转化为 (±)-洋地黄糖 (3)，而次要的抗、顺加合物 (±)-27 也转化为 (±)-橄榄糖 (4) ）。 (±)-10与乙酸叔丁酯阴离子的反应主要产生反加合物(±)-23，其转化为(±)-1,5-二脱氧己糖醇(25)。或者，由反式-(2,3)-环氧丁酸酯衍生的2,3-syn-2-叔丁基二甲基硅氧基-3-对甲氧基苯氧基丁醛衍生物[syn-B, (±)-14]的反应 (1)与碳亲核试剂（In辅助烯丙基阴离子）提供约。顺式、反式加合物E[(±)-32或(±)-34]和顺式、顺式加合物F[(±)-33或(±)-35]的1:1混合物。分离该混合物后，(±)-34和(±)-35分别转化为(±)-寡糖(5)和(±)-牛维糖(6)。
• Synthesis of 2,6-Dideoxysugars via Ring-Closing Olefinic Metathesis
  作者：Peter R. Andreana、Jason S. McLellan、Yongchen Chen、Peng George Wang

  DOI：10.1021/ol026710m

  日期：2002.10.1

  graphicGrubbs' RuCl2(=CHPh)(PCy3)(2) (catalyst 1) and RuCl2(=CHPh)(PCy3)(IMess) (catalyst 2) complexes have been successfully utilized in the construction of beta,gamma-unsaturated delta-lactones containing various substitution patterns of methyl groups. Asymmetric dihydroxylation followed by reduction leads to 3,4-cis-dihydroxy-2,6-dideoxypyranoses, which have proven to play very important biological roles as key components of natural products.