(2R,3S)-2-(tert-butoxycarbonyl)amino-3-methoxycarbonyl-3-methylbutanal | 134440-97-4

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 脂肪酰基
• 英文名称: (2R,3S)-2-(tert-butoxycarbonyl)amino-3-methoxycarbonyl-3-methylbutanal
• 英文别名: (2R,3S)-2-(tert-butoxycarbonyl)amino-3-methoxycarbonyl-butanal；(2R,3S)-N-tert-butoxycarbonyl-2-amino-3-carbomethoxybutanal；methyl (2S,3R)-3-(N-Boc-amino)-4-oxo-2-methylbutanoate；methyl (2S,3R)-2-methyl-3-[(2-methylpropan-2-yl)oxycarbonylamino]-4-oxobutanoate
• CAS: 134440-97-4
• 化学式: C₁₁H₁₉NO₅
• 分子量: 245.276
• InChiKey: MFWVYMBXFPPUID-YUMQZZPRSA-N

物化性质

• 沸点：
  353.9±37.0 °C(Predicted)
• 密度：
  1.094±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  0.9
• 重原子数：
  17
• 可旋转键数：
  7
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.73
• 拓扑面积：
  81.7
• 氢给体数：
  1
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  (2R,3S)-2-(tert-butoxycarbonyl)amino-3-methoxycarbonyl-3-methylbutanal 在 chromium dichloride 、 2,3,5-三甲基吡啶 、 lithium hydroxide 、 四(三苯基膦)钯 、 thallium (I) ethoxide 、 溶剂黄146 、 N,N'-二环己基碳二亚胺 、 N-[(dimethylamino)-3-oxo-1H-1,2,3-triazolo[4,5-b]pyridin-1-yl-methylene]-N-methylmethanaminium hexafluorophosphate 、 锌 作用下， 以 四氢呋喃 、 1,4-二氧六环 、 水 、 乙酸乙酯 、 N,N-二甲基甲酰胺 为溶剂， 反应 114.0h， 生成 methyl (2R,3S)-2-[[(2S)-2-[[(2R)-2-[2-[[(4R)-5-methoxy-4-[[(2S,3S,4E,6E,8S,9S)-9-methoxy-2,6,8-trimethyl-3-[(2-methylpropan-2-yl)oxycarbonylamino]-10-phenyldeca-4,6-dienoyl]amino]-5-oxopentanoyl]-methylamino]prop-2-enoylamino]propanoyl]amino]-4-methylpentanoyl]amino]-3-methyl-4-oxo-4-[[(2S)-1-oxo-1-(2,3,4,5,6-pentafluorophenoxy)propan-2-yl]amino]butanoate
  参考文献：
  名称：

  丝氨酸-苏氨酸磷酸酶抑制剂微囊藻毒素-LA的全合成

  摘要：

  由激酶和磷酸酶介导的可逆蛋白磷酸化是细胞的主要控制元件。有多种有毒的天然产物会抑制某些磷酸酶，从而破坏正常的生化途径。这些毒素可用于剖析与这些酶中的每一种相关的个体生化途径。本文描述了一种此类毒素的首次全合成，即环状七肽微囊藻毒素-LA。该合成具有收敛路线，可用于寻找选择性磷酸酶抑制剂的类似物制备。描述了一种不寻常的氨基酸 Adda 的新途径，它通过 Suzuki 偶联反应结合了有效的非对映选择性天冬氨酸烷基化和二烯合成。

  DOI：

  10.1021/ja961683e
• 作为产物：
  描述：

  methyl (2S,3R)-3-(N-Boc-amino)-4-(tert-butyldimethylsilyloxy)-2-methyl-butanoate 在 N-溴代丁二酰亚胺(NBS) 、 草酰氯 作用下， 以 二氯甲烷 、 二甲基亚砜 为溶剂， 反应 3.0h， 生成 (2R,3S)-2-(tert-butoxycarbonyl)amino-3-methoxycarbonyl-3-methylbutanal
  参考文献：
  名称：

  Total Synthesis of Motuporin and 5-[l-Ala]-Motuporin

  摘要：

  Total synthesis of the cyclic peptide hepatotoxin motuporin is described, including an efficient synthesis of the constituent amino acid Adda. Three strategies to motuporin are outlined with their relative strengths and weaknesses. Cyclization of the linear peptide precursor was found to proceed moderately well for peptides containing the N-methyldehydrobutyrine residue masked as a threonine, but significant C-terminal epimerization occurred in the presence of the dehydroamino acid. Replacement of the N-methyldehydrobutyrine residue by L-alanine was explored to assess the contribution of this dehydroamino acid to the biochemical activity of motuporin. Some epimerization also was observed during cyclization of the alanine-containing peptide. Synthetic motuporin and both isomers of 5-[L-Ala]-motuporin inhibit the activity of protein phosphatase-l (PP1) in rat adipocyte lysates with comparable IC50 values. These results indicate that the N-methyldehydrobutyrine residue is not essential for PP1 inhibition.

  DOI：

  10.1021/jo982145i

文献信息

• Stereoconvergent synthesis of (2S,3S,8S,9S,4E,6E)-N-Boc-ADDA starting from (S)-serine and (S)-phenyllactic acid
  作者：Fabiana D'Aniello、André Mann、Angèle Schoenfelder、Maurizio Taddei

  DOI：10.1016/s0040-4020(96)01056-3

  日期：1997.1

  β-amino acid N-Boc-ADDA is prepared following a disconnection of the CC bond between the two E,E double bonds. The stereochemistry of the two synthons was controlled using the alkylation of chiral bromoallenes derived from naturally occurring (S)-serine and (S)-phenyllactic acid. The cupration of bromoallenes derived from (S)-serine also provides a general method for the synthesis of chiral β-alkylated

  重要的天然β-氨基酸N-Boc-ADDA是在两个E，E双键之间的CC键断开后制备的。使用衍生自天然存在的（S）-丝氨酸和（S）-苯基乳酸的手性溴代烯烷基化来控制两个合成子的立体化学。衍生自（S）-丝氨酸的溴丙二烯的铜化也提供了合成手性β-烷基化的天冬氨酸衍生物的通用方法。
• Stereocontrolled synthesis of (2S, 3S, 8S, 9S)-3-amino-9-methoxy-2,6,8-trimethyl-10-phenyldeca-4E,6E-dienoic acid (ADDA), the characteristic amino acid of microcystins and nodularin
  作者：Mark F. Beatty、Clive Jennings-White、Mitchell A. Avery

  DOI：10.1039/c39910000351

  日期：——

  (4R,5S)-4-Methyl-5-phenyloxazolidin-2-one was used as a chiral template to construct the 8S and 9S chiral centres of (2S,3S,8S,9S)-3-amino-9-methoxy-2,6,8-trimethyl-10-phenyldeca-4,6-dienoic acid (ADDA), the 2S and 3S centres were derived from D-aspartic acid.

  以（4 R，5 S）-4-甲基-5-苯基恶唑烷丁-2-酮为手性模板，构建（2 S，3 S，8 S，9 S）-的8 S和9 S手性中心。3-氨基-9-甲氧基-2,6,8-三甲基-10-苯基癸-4,6-二烯酸（ADDA）的2 S和3 S中心衍生自D-天门冬氨酸。
• Stereocontrolled synthesis of (2S,3S,8S,9S,4E,6E)-3-amino-9-methoxy-2,6,8-trimethyl-10-phenyldeca-4,6-dienoic acid (Adda), the amino acid characteristic of microcystins and nodularin
  作者：Vlark F. Beatty、Clive Jennings-White、Mitchell A. Avery

  DOI：10.1039/p19920001637

  日期：——

  (4R,5S)-4-Methyl-5-phenyloxazolindin-2-one has been used as a chiral template to construct the 8S and 9S chiral centres of (2S,3S,8S,9S)-3-amino-9-methoxy-2,6,8-trimethyl-10-phenyldeca-4,6-dienoic acid (Adda), the 2S and 3S centres being derived from D-aspartic acid.

  （4 R，5 S）-4-甲基-5-苯基恶唑啉丁-2-一已被用作手性模板来构建（2 S，3 S，8 S，9 S）的8 S和9 S手性中心-3-氨基-9-甲氧基-2,6,8-三甲基-10-苯基癸基-4,6-二烯酸（Adda），其2 S和3 S中心衍生自D-天门冬氨酸。
• A new stereoselective route to (2S, 3S, 8S, 9S, 4E, 6E)-3-amino-9-methoxy-2, 6, 8-trimethyl-10-phenyldeca-4, 6-dienoic acid (Adda)
  作者：Hong Yong Kim、Peter L. Toogood

  DOI：10.1016/0040-4039(96)00282-1

  日期：1996.4

  N-Boc-Adda has been prepared in 15 steps and 9% overall yield from the readily available alcohol, 3-pentyne-2-ol, employing a route that includes two Claisen rearrangements.

  使用包括两个克莱森重排的途径，由15种步骤制备N -Boc-Adda，总产率为9％，由现成的醇3-pentyne-2-ol制备。
• 1,3-Stereocontrol with Bromoallenes. Synthesis of <i>N</i>-Boc-ADDA, the Unique Amino Acid Present in Several Inhibitors of Serine/Threonine Phosphatases
  作者：F. D'Aniell、A. Mann、M. Taddei

  DOI：10.1021/jo9605004

  日期：1996.1.1