3,4-bis-(tert-butyldimethylsilyl)-1,5-anhydro-2,6-dideoxy-L-lyxo-hex-1-enitol | 101915-63-3

• 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: 3,4-bis-(tert-butyldimethylsilyl)-1,5-anhydro-2,6-dideoxy-L-lyxo-hex-1-enitol
• 英文别名: 3,4-bis-O-(t-butyldimethylsilyl)-L-fucal；3,4-di-O-tert-butyldimethylsilyl-L-fucal；2,6-anhydro-3,4-bis-O-[tert-butyl(dimethyl)silyl]-1,5-dideoxy-L-arabino-hex-5-enitol；tert-butyl-[[(2S,3R,4S)-3-[tert-butyl(dimethyl)silyl]oxy-2-methyl-3,4-dihydro-2H-pyran-4-yl]oxy]-dimethylsilane
• CAS: 101915-63-3
• 化学式: C₁₈H₃₈O₃Si₂
• 分子量: 358.669
• InChiKey: AWUUEOFMBNBQBH-HRCADAONSA-N

物化性质

• 沸点：
  349.1±42.0 °C(Predicted)
• 密度：
  0.91±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  5.7
• 重原子数：
  23
• 可旋转键数：
  6
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.89
• 拓扑面积：
  27.7
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  3,4-bis-(tert-butyldimethylsilyl)-1,5-anhydro-2,6-dideoxy-L-lyxo-hex-1-enitol 在 N-溴代丁二酰亚胺(NBS) 、 偶氮二异丁腈 、 三正丁基氢锡 作用下， 以 乙腈 、 苯 为溶剂， 反应 3.5h， 生成 (5R,6R,7R)-5-O-(t-butyldimethylsilyl)-<3,4-bis-O-(t-butyldimethylsilyl)-2-deoxy-α-L-fucosyl>-6-ethyl-5,7-dihydroxy-3-octanone
  参考文献：
  名称：

  Elaiophylin (Azalomycin B) 的全合成

  摘要：

  抗生素 elaiophylin (1) 已首先通过收敛路线合成，包括 (5R,6R,7R)-5-O-[2-deoxy-3,4-bis-O-(isopropyldimethylsilyl)-α-L-吡喃岩藻糖基]-6-乙基-7-O-(二乙基异丙基甲硅烷基)-5,7-二羟基-3-辛酮 (25f) 和 (7S,8S,15S,16S:3E,5E,11E,13E)-8,16-双[(1R)-1-甲酰基乙基]-7,15-二甲基-1,9-dioxa-3,5,11,13-cyclohexadecatetraene-2,10-dione (3)，然后脱甲硅烷基化。由 D-葡萄糖和 2-脱氧-L-岩藻糖合成适当的 O-保护链段 25f 和大环二醛 3。

  DOI：

  10.1246/bcsj.61.2369
• 作为产物：
  描述：

  Benzoic acid (2S,3S,4S,6S)-4-acetoxy-2-bromomethyl-6-methoxy-tetrahydro-pyran-3-yl ester 在 2,6-二甲基吡啶 、 palladium on activated charcoal 2,6-二甲基吡啶 、 lithium aluminium tetrahydride 、 氢气 、 silver fluoride 作用下， 生成 3,4-bis-(tert-butyldimethylsilyl)-1,5-anhydro-2,6-dideoxy-L-lyxo-hex-1-enitol
  参考文献：
  名称：

  Synthetic studies on antibiotic macrodiolide: Synthesis of the a-segment of elaiophylin

  摘要：

  DOI：

  10.1016/s0040-4039(00)83909-x

文献信息

• Total synthesis of elaiophylin (azalomycin B)
  作者：Kazunobu Toshima、Kuniaki Tatsuta、Mitsuhiro Kinoshita

  DOI：10.1016/s0040-4039(00)85053-4

  日期：——

  Antibiotic elaiophylin has been first synthesized by a convergent route involving aldol condensation between (5R,6R,7R)-5-0-[2′-deoxy-3′,4′-di-0-(dimethylisopropylsilyl)-α-L-fucopyranosyl]-6-ethyl-7-0-(diethylisopropylsilyl)-5,7-dihydroxy-3-octanone and (7S,8S,15S, 16S) - (3E, 5E, 11E, 13E) -8,16-bis [ (1 ′R) -1′ -formylethyl] -7,15-dimethyl-1, 9-dioxacyclohexadeca-3,5, 11,13-tetraene-2,10-dione ,

  抗生素鞣花素已首先通过收敛途径合成，该途径涉及（5 R，6 R，7 R）-5-0- [2'-脱氧-3'，4'-di-0-（二甲基异丙基甲硅烷基）-α之间的羟醛缩合-L-呋喃核糖基] -6-乙基-7-0-（二乙基异丙基甲硅烷基）-5,7-二羟基-3-辛酮和（7 S，8 S，15 S，16 S）-（3 E，5 E，11 ê，13 ë）-8,16 -双[（1- 'R）-1'-formylethyl] -7,15 -二甲基- 1,9-dioxacyclohexadeca-3,5，11,13四烯2,10-二酮，然后进行去甲硅烷基化。细分和由D-葡萄糖和2-脱氧-L-岩藻糖合成。
• Stereoselective Glycosylations of a Family of 6-Deoxy-1,2-glycals Generated by Catalytic Alkynol Cycloisomerization
  作者：Frank E. McDonald、K. Subba Reddy、Yolanda Díaz

  DOI：10.1021/ja994229u

  日期：2000.5.1

  Photolysis of 0.25 equiv of W(CO)6 in the presence of tertiary amines (triethylamine or DABCO) and highly functionalized terminal alkynyl alcohols catalyzes single-step, high-yield cycloisomerization to endocyclic enol ethers. This transformation is general for each diastereomeric 3,4-bissilyl ether of 5-hydroxy-1-hexyne, leading to enantio- and diastereoselective syntheses of each isomer of 6-deoxy-1

  在叔胺（三乙胺或 DABCO）和高度官能化的末端炔醇存在下，0.25 当量的 W(CO)6 的光解催化单步、高产率环异构化为内环烯醇醚。这种转化对于 5-羟基-1-己炔的每个非对映异构 3,4-双甲硅烷基醚是通用的，导致 6-脱氧-1,2-乙二醇的每个异构体的对映选择性和非对映选择性合成。每种糖基非对映异构体的立体选择性糖基化也已得到证明，并已应用于 d-洋地黄毒苷-β-4-d-洋地黄糖苷的制备。
• Synthesis of the glycosyl lactol moiety of halichoblelide
  作者：Yohsuke Satoh、Takashi Nakahata、Shigefumi Kuwahara

  DOI：10.1016/j.tet.2007.08.100

  日期：2007.11

  The enantioselective synthesis of the 2-deoxy-alpha-L-fucosyl lactol moiety of halichoblelide, a potent cytotoxin isolated from an actinomycete of marine origin, was achieved using a diastereoselective addition of a dithianyl anion to a chiral aldehyde intermediate and a stereoselective glycosidation of a hydroxy lactone intermediate derived from the addition product with a protected L-fucal as the key steps. (c) 2007 Elsevier Ltd. All rights reserved.
• C-Glycosylanthraquinone synthesis: total synthesis of vineomycinone B2 methyl ester
  作者：Marcus A. Tius、Jorge Gomez-Galeno、Xue Qin Gu、Javid H. Zaidi

  DOI：10.1021/ja00015a035

  日期：1991.7

  A synthesis of substituted anthraquinones has been developed. Commercially available anthrarufin and 1,8-dihydroxyanthraquinone were converted to the corresponding (methoxymethoxy)anthracenes. Directed metalation followed by stannylation produced stable intermediates that were either alkylated, arylated, acylated, and/or C-glycosylated. The value of this new methodology was demonstrated by the triply convergent total synthesis of vineomycinone B2 methyl ester, a representative C-glycosylanthraquinone antibiotic.
• Selective silylation of 6-deoxyglycals
  作者：Derek Horton、Waldemar Priebe、Oscar Varela

  DOI：10.1016/s0008-6215(00)90680-3

  日期：1985.12