3-<(tert-Butoxycarbonyl)amino>-4-O-(tert-butyldiphenylsilyl)-3-deoxy-3-N,2-O-isopropylidene-D-threose | 138319-97-8

• 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-<(tert-Butoxycarbonyl)amino>-4-O-(tert-butyldiphenylsilyl)-3-deoxy-3-N,2-O-isopropylidene-D-threose
• 英文别名: (4R,5S)-3-N-tert-butoxycarbonyl-4-tert-butyldiphenylsilyloxymethyl-5-formyl-2,2-dimethyl-1,3-oxazolidine；tert-butyl (4R,5S)-4-[[tert-butyl(diphenyl)silyl]oxymethyl]-5-formyl-2,2-dimethyl-1,3-oxazolidine-3-carboxylate
• CAS: 138319-97-8
• 化学式: C₂₈H₃₉NO₅Si
• 分子量: 497.707
• InChiKey: CTPHYLQRPPHEPN-DNQXCXABSA-N

物化性质

• 沸点：
  536.4±50.0 °C(Predicted)
• 密度：
  1.11±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4.5
• 重原子数：
  35
• 可旋转键数：
  9
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  65.1
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  3-<(tert-Butoxycarbonyl)amino>-4-O-(tert-butyldiphenylsilyl)-3-deoxy-3-N,2-O-isopropylidene-D-threose 在 镍 2,6-二甲基吡啶 、 copper(l) iodide 、 氢气 作用下， 以 乙醇 、 二氯甲烷 、 氯仿 为溶剂， -50.0~-30.0 ℃ 、303.98 kPa 条件下， 反应 29.25h， 生成 (4R,5R)-4-(tert-Butyl-diphenyl-silanyloxymethyl)-2,2-dimethyl-5-((S)-1-methyl-3-trifluoromethanesulfonyloxy-propyl)-oxazolidine-3-carboxylic acid tert-butyl ester
  参考文献：
  名称：

  Formal synthesis of an unusual amino acid component of cyclosporin, involving stereocontrolled nucleophilic 1,4-addition

  摘要：

  A syn-(2R)-amino-1,3,4-butanetriol derivative, readily available from D-isoascorbic acid, was utilized for the synthesis of MeBmt found in the immunosuppressive undecacyclopeptide cyclosporin. This new strategy involves diastereoselective nucleophilic 1,4-addition of lithium dimethylcuprate to a chiral alpha,beta-unsaturated aldehyde, and elaboration of the terminal double bond, by Takai or Wittig method for the MeBmt or its 6Z-isomer, respectively. (C) 1997 Elsevier Science Ltd.

  DOI：

  10.1016/s0957-4166(97)00164-x
• 作为产物：
  描述：

  (1S,2R)-2-<(tert-Butoxycarbonyl)amino>-3-<(tert-butyldiphenylsilyl)oxy>-1-hydroxy-2-N,1-O-isopropylidene-1-(1,3-thiazol-2-yl)propane 在 sodium tetrahydroborate 、 4 A molecular sieve 、 copper(II) oxide 、 copper dichloride 作用下， 以 乙腈 为溶剂， 反应 1.08h， 生成 3-<(tert-Butoxycarbonyl)amino>-4-O-(tert-butyldiphenylsilyl)-3-deoxy-3-N,2-O-isopropylidene-D-threose
  参考文献：
  名称：

  Total Synthesis of (+)-Galactostatin. An Illustration of the Utility of the Thiazole-Aldehyde Synthesis

  摘要：

  The natural aza sugar (+)-galactostatin (+)-1 has been prepared from D-serine by sequential installation of chiral 1C and 2C units employing thiazole-based reagents. Thus, the D-serine-derived methyl ester 3 was transformed by 2-thiazolyllithium (4) into the thiazolyl amino ketone 5 which, via syn stereoselective carbonyl reduction and thiazolyl-to-formyl conversion, gave the first key intermediate, the alpha-hydroxy beta-amino aldehyde 10. The olefination of this compound by [(2-thiazolyl)-methylene]triphenylphosphorane (14) followed by osmium tetroxide cis dihydroxylation of the resulting alkene E-16 and cleavage of the thiazole ring produced the second key intermediate, the amino- and hydroxyl-protected 5-deoxy-5-amino- D-galactose 20. The removal of all protecting groups of this compound afforded the target aza sugar (+)-1 in 17.3% overall yield from 3.

  DOI：

  10.1021/jo00120a017

文献信息

• Stereocontrolled total synthesis of galactostatin from serine
  作者：Alessandro Dondoni、Pedro Merino、Daniela Perrone

  DOI：10.1039/c39910001576

  日期：——

  An efficient stereoselective total synthesis of (–)-galactostatin (–)-1 from N-tert-butoxycarbonyi-2,3-isopropylidene L-serine methyl ester (21% overall yield) is described via thiazole intermediates serving as protected aldehydes; the parallel synthesis of the natural antipole (+)-1 starts from D-serine.

  介绍了通过噻唑中间体作为受保护的醛，从 N-叔丁氧羰基-2,3-异亚丙基 L-丝氨酸甲酯高效立体选择性全合成 (-)-galactostatin (-)-1（总收率 21%）的方法；从 D-丝氨酸开始平行合成天然反极 (+)-1。
• Synthesis of (2S,3R)-3-amino-2-hydroxydecanoic acid and (3R,4R)-3-amino-4-hydroxyazepane from D-isoascorbic acid
  作者：Arounarith Tuch、Michèle Sanière、Yves Le Merrer、Jean-Claude Depezay

  DOI：10.1016/0957-4166(96)00381-3

  日期：1996.10

  advantage of the high functionality of an enantiopure protected syn-2R-amino-1,3,4-triol derivative, easily available on a multigram scale from D-isoascorbic acid, several biologically active compounds have been synthesized such as the (2S,3R)-3-amino-2-hydroxydecanoic acid (AHDA), the N-terminal moiety of microginin, and the (3R,4R)-3-amino-4-hydroxyazepane, the ophiocordin and balanol core structure.

  利用对映体保护的syn -2 R-氨基-1,3,4-三醇衍生物的高功能性（可轻松从D-异抗坏血酸以克数购得），合成了几种生物活性化合物，例如（2 S，3 R）-3-氨基-2-羟基癸酸（AHDA），微ginin的N末端部分和（3 R，4 R）-3-氨基-4-羟基氮杂环庚烷，ophiocordin和balanol核心结构。
• Enantiopure aminotriol from d-isoascorbic acid synthesis of
  作者：Arounarith Tuch、Michèle Sanière、Yves Le Merrer、Jean-Claude Depezay

  DOI：10.1016/0957-4166(96)00087-0

  日期：1996.3

  Enantiopure suitably N,O-protected aminotriol has been prepared from D-isoascorbic acid. The utility of this homochiral building block in the synthesis of (2R,3R)-D-threo-C-18-sphingosine is described via a Wittig reaction on a N,O-protected beta-amino-alpha-hydroxyaldehyde. (C) 1996 Elsevier Science Ltd
• Total Synthesis of (+)-Galactostatin. An Illustration of the Utility of the Thiazole-Aldehyde Synthesis
  作者：Alessandro Dondoni、Daniela Perrone

  DOI：10.1021/jo00120a017

  日期：1995.7

  The natural aza sugar (+)-galactostatin (+)-1 has been prepared from D-serine by sequential installation of chiral 1C and 2C units employing thiazole-based reagents. Thus, the D-serine-derived methyl ester 3 was transformed by 2-thiazolyllithium (4) into the thiazolyl amino ketone 5 which, via syn stereoselective carbonyl reduction and thiazolyl-to-formyl conversion, gave the first key intermediate, the alpha-hydroxy beta-amino aldehyde 10. The olefination of this compound by [(2-thiazolyl)-methylene]triphenylphosphorane (14) followed by osmium tetroxide cis dihydroxylation of the resulting alkene E-16 and cleavage of the thiazole ring produced the second key intermediate, the amino- and hydroxyl-protected 5-deoxy-5-amino- D-galactose 20. The removal of all protecting groups of this compound afforded the target aza sugar (+)-1 in 17.3% overall yield from 3.
• Formal synthesis of an unusual amino acid component of cyclosporin, involving stereocontrolled nucleophilic 1,4-addition
  作者：Arounarith Tuch、Michèle Saniìere、Yves Le Merrer、Jean-Claude Depezay

  DOI：10.1016/s0957-4166(97)00164-x

  日期：1997.5

  A syn-(2R)-amino-1,3,4-butanetriol derivative, readily available from D-isoascorbic acid, was utilized for the synthesis of MeBmt found in the immunosuppressive undecacyclopeptide cyclosporin. This new strategy involves diastereoselective nucleophilic 1,4-addition of lithium dimethylcuprate to a chiral alpha,beta-unsaturated aldehyde, and elaboration of the terminal double bond, by Takai or Wittig method for the MeBmt or its 6Z-isomer, respectively. (C) 1997 Elsevier Science Ltd.