(2R,3S)-4-(tert-butyldiphenylsilyloxy)-2,3-epoxybutan-1-al | 131486-44-7

• 分子结构分类: 有机化合物 - 有机金属化合物 - 有机类金属化合物
• 英文名称: (2R,3S)-4-(tert-butyldiphenylsilyloxy)-2,3-epoxybutan-1-al
• 英文别名: (2R,3S)-3-[[tert-butyl(diphenyl)silyl]oxymethyl]oxirane-2-carbaldehyde
• CAS: 131486-44-7
• 化学式: C₂₀H₂₄O₃Si
• 分子量: 340.494
• InChiKey: DPYJVPLZFFROJT-OALUTQOASA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.53
• 重原子数：
  24
• 可旋转键数：
  7
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.35
• 拓扑面积：
  38.8
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  (2R,3S)-4-(tert-butyldiphenylsilyloxy)-2,3-epoxybutan-1-al 在 吡啶 、 4 A molecular sieve 、 硫酸 、 氯化二乙基铝 作用下， 以 二氯甲烷 、 甲苯 为溶剂， 反应 55.0h， 生成 (-)-arabino-(4S,5S,6S)-7-(tert-butyldiphenylsiloxy)hept-1-ene-4,5,6-triol 4,5-carbonate
  参考文献：
  名称：

  A stereochemically general synthesis of 2-deoxyhexoses via the asymmetric allylboration of 2,3-epoxy aldehydes

  摘要：

  A stereochemically general strategy for the synthesis of 2-deoxyhexoses is described. This new approach involves the asymmetric allylboration of epoxy aldehydes 12 and 13, prepared via the Sharpless asymmetric epoxidation reaction, as a means of establishing the stereochemistry of the sugar backbone. Thus, the matched double asymmetric allylborations of 12 and 13 using tartrate allylboronates (R,R)- and (S,S)-7, respectively, provide erythro epoxy alcohols 14 and 16 with excellent diastereoselectivity ( > 96:4) and enantioselectivity (greater-than-or-equal-to 96% ee). The mismatched double asymmetric reactions of 12 and 13 using (S,S)- and (R,R)-7, respectively, provided the diastereomeric threo epoxy alcohols 15 and 17 with lower (ca. 75:25) but still synthetically useful selectivity. The enantiomeric purity of the major diastereomer in each of these reactions was determined to be greater than that of the epoxy aldehyde precursors. Epoxy alcohols 14 and 16 were converted with excellent selectivity to the l-arabino (21) and l-xylo (26) tetrols via neighboring group assisted alpha-substitution reactions of the derived phenylurethane derivatives 18 and 23. Stereochemically complementary beta-opening reactions were accomplished by treating primary alcohols 38, 40, 42, and 44 [prepared from 14-17, respectively, by ethoxyethylation of C(4)-OH and removal of the C(7)-tert-butyldiphenylsilyl (TBDPS) ethers] with NaOH in aqueous t-BuOH at reflux. Acid-catalyzed hydrolysis of the C(4)-ethoxyethyl ethers then provided tetrols d-35 (from 14), d-21 (from 15), d-30 (from 16), and d-26 (from 17), each with excellent stereoselectivity. These tetrols were isolated and fully characterized as the tetraacetate derivatives 36, 22, 31, and 27, respectively. These beta-opening reactions proceed by way of an epoxide migration (29 to 33) that inverts the stereochemistry at C(6) and activates C(7) toward nucleophilic attack. It is necessary that the C(4) hydroxyl be protected in three of the four stereoisomeric series to minimize competitive epoxide migration pathways (cf. 29 to 32a). arabino tetrol 21 and lyxo tetrol 30 were converted to 2-deoxyglucose and 2-deoxygalactose, respectively, by a standard ozonolytic sequence and then to 2-deoxyglucitol pentaacetate (45) and 2-deoxygalactitol pentaacetate (46) via NaBH4 reduction of the 2-deoxy sugars, thereby confirming all stereochemical assignments. The epoxide beta-opening technology was also applied to epoxy benzyl ether 47 (prepared from 14) and epoxy BOM ether 49 (deriving from 16). These reactions provide tetrol derivatives 48 and 50, respectively, in which the C(4)- and C(5)-hydroxyl functionality are suitably differentiated for use in subsequent synthetic sequences.

  DOI：

  10.1021/jo00004a053
• 作为产物：
  描述：

  (E)-4-(tert-butyldiphenylsilyloxy)-2-buten-1-ol 在 titanium(IV) isopropylate 、 叔丁基过氧化氢 、 D-(-)-酒石酸二异丙酯 、 3 A molecular sieve 、 三氧化硫吡啶 、 二甲基亚砜 、 三乙胺 作用下， 以 二氯甲烷 为溶剂， 反应 36.5h， 生成 (2R,3S)-4-(tert-butyldiphenylsilyloxy)-2,3-epoxybutan-1-al
  参考文献：
  名称：

  除烯醇锂之外的手性α，β-环氧醛的非对映体分化

  摘要：

  已经研究了酯酸锂与手性α，β-环氧醛2a–2f的醛醇缩合反应。反应以非对映体优先进行，有利于抗异构体（anti：syn≈4：1），在顺式α，β-环氧-醛2a–2c的情况下，温度和烯醇过量的协同作用可以大大增强反应（反：syn 13：1）。Felkin-Ahn模型可以解释在不对称感应下获得的结果。

  DOI：

  10.1016/s0040-4020(01)82375-9

文献信息

• Diastereoface differentiation in addition of lithium enolates to chiral α,β-epoxyaldehydes
  作者：Jean-Marc Escudier、Michel Baltas、Liliane Gorrichon

  DOI：10.1016/s0040-4020(01)82375-9

  日期：1993.6

  aldolisation reaction of lithium ester enolates with chiral α,β-epoxyaldehydes 2a–2f has been investigated. The reaction proceeds with diastereofacial preference in favour of the anti isomer (anti:syn ≈ 4:1) and can be greatly enhanced in the case of cis α,β-epoxy-aldehydes 2a–2c by a synergic effect of temperature and enolate excess (anti:syn 13:1). The Felkin-Ahn model can explain the results obtained

  已经研究了酯酸锂与手性α，β-环氧醛2a–2f的醛醇缩合反应。反应以非对映体优先进行，有利于抗异构体（anti：syn≈4：1），在顺式α，β-环氧-醛2a–2c的情况下，温度和烯醇过量的协同作用可以大大增强反应（反：syn 13：1）。Felkin-Ahn模型可以解释在不对称感应下获得的结果。
• Addition of lithium ethyl fluoroacetate to cis and trans α,β-epoxyaldehydes. Access to C2 fluorinated butyrolactones
  作者：Magalie Collet、Michel Baltas、Alexandre Martinez、Cécile Dehoux-Baudoin、Liliane Gorrichon

  DOI：10.1016/s0040-4039(03)00145-x

  日期：2003.2

  The aldolisation reaction of lithium ethyl fluoroacetate with cis and trans α,β-epoxyaldehydes in their racemic forms proceeds with good C3-OH diastereoselectivity and much less at the C2-F carbon atom. A two-step reaction on the major aldol compounds (iodination, lactonisation) led to racemic functionalised C2 fluorinated lactones, possessing a C2/C3cis relationship between the fluorine and hydroxyl

  氟乙酸乙酯与外消旋形式的顺式和反式α，β-环氧醛的醛醇缩合反应具有良好的C 3 -OH非对映选择性，而在C 2 -F碳原子上的选择性低得多。主要醛醇化合物的两步反应（碘化，内酯化）导致外消旋官能化的C 2氟化内酯，在氟和羟基之间具有C 2 / C 3顺式关系。
• Boron trifluoride as a promoter and fluoride donor in the aldol reaction of trans α,β-epoxyaldehydes. Access to 5- and 6-fluoro heptulosonic ester analogues
  作者：Yvan Ruland、Chantal Zedde、Michel Baltas、Liliane Gorrichon

  DOI：10.1016/s0040-4039(99)01442-2

  日期：1999.10

  A direct synthesis of 5- and 6-fluoro heptulosonic esters is achieved by reaction of trans α,β-epoxyaldehydes with 2-(trimethylsilyloxy)acrylate in presence of BF3·Et2O.

  通过在BF 3 ·Et 2 O存在下反式α，β-环氧醛与2-（三甲基甲硅烷基氧基）丙烯酸酯反应，可以直接合成5和6-氟氟代磺酸磺酸酯。
• Stereoselective synthesis of (+)-1-deoxyaltronojirimycin
  作者：Giuliana Righi、Emanuela Mandic’、Ilaria Tirotta、Gaia Clara Mercedes Naponiello、Carla Sappino、Cristina Marucci、Michela Tomei、Paolo Bovicelli

  DOI：10.1080/14786419.2015.1131983

  日期：2016.7.17

  A stereocontrolled, facile and high-yield approach for producing (+)-altroDNJ, has been developed starting from the inexpensive commercial cis 2-butene-1,4-diol. Sharpless epoxidation and a subsequent dihydroxylation were used for the introduction of all stereocentres; finally, the ring closure under basic conditions afforded the piperidine heterocycle.

  从廉价的商业化的顺式2-丁烯-1,4-二醇开始，开发了立体控制的，容易的且高产率的方法来生产（+）- altro DNJ 。尖锐的环氧化和随后的二羟基化被用于引入所有立体中心。最后，在碱性条件下的闭环提供了哌啶杂环。
• Asymmetric Total Synthesis of the Putative Structure of Diplopyrone
  作者：Saurabh Maity、Suresh Kanikarapu、Kanakaraju Marumudi、Ajit C. Kunwar、Jhillu S. Yadav、Debendra K. Mohapatra

  DOI：10.1021/acs.joc.7b00086

  日期：2017.5.5

  The first asymmetric total synthesis of the putative structure of diplopyrone was achieved in 17 linear steps starting from cis-1,4-butene-diol. The synthetic route features iodine-catalyzed tandem isomerization followed by C–O and C–C bond formation reaction strategy developed by our own group to construct the trans-2,6-disubstituted dihydropyran ring, asymmetric α-aminoxylation reaction, and Still–Gennari

  从17线性步骤开始，从顺式-1,4-丁烯二醇开始的第一个假定的结构的双吡咯酮的第一个不对称的全合成。合成途径的特征是碘催化的串联异构化，然后由我们自己的小组开发了C–O和C–C键形成反应策略，以构建反式-2,6-二取代的二氢吡喃环，不对称的α-氨基羟化反应和Still-Gennari （Z）-选择性烯烃化反应。仔细比较1 H和13 C NMR光谱数据以及化合物2在三氟乙醇中的UV和圆二色性光谱的研究表明，假定的双吡喃酮结构6-[（1 S）-1-羟乙基] -2,4a（S），6（R），8a（S）-四氢吡喃[3,2 - b ] pyran-2-one}需要修订。