dibutyl diazomalonate | 169825-18-7

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羧酸及其衍生物
• 英文名称: dibutyl diazomalonate
• 英文别名: di-n-butyl α-diazomalonate；dibutyl 2-diazomalonate；Dibutyl 2-diazopropanedioate
• CAS: 169825-18-7
• 化学式: C₁₁H₁₈N₂O₄
• 分子量: 242.275
• InChiKey: BLMJVOXNOMSQFP-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.2
• 重原子数：
  17
• 可旋转键数：
  10
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.73
• 拓扑面积：
  54.6
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  dibutyl diazomalonate 、 芴甲氧羰基-L-酪氨酸-叔丁酯 在 dirhodium tetraacetate 作用下， 以 苯 为溶剂， 以68%的产率得到dibutyl 2-[4-[(2S)-2-(9H-fluoren-9-ylmethoxycarbonylamino)-3-[(2-methylpropan-2-yl)oxy]-3-oxopropyl]phenoxy]propanedioate
  参考文献：
  名称：

  L-O-(2-malonyl)tyrosine (L-OMT) a new phosphotyrosyl mimic suitably protected for solid-phase synthesis of signal transduction inhibitory peptides

  摘要：

  A new phosphotyrosyl (pTyr) mimic L-O-(2-malonyl)tyrosine (L-OMT, 4) utilizes a malonyl structure in place of the parent phosphate group. This compound is stable to protein-tyrosine phosphatases and has advantages over phosphonate-based pTyr mimics in that protection of the malonyl group as its diester allows passage of the OMT across cell membranes, with subsequent esterase-mediated liberation of the free diacid once inside cells. Herein is reported the synthesis of N-alpha-Fmoc-L-OMT-O,O-(tert-butyl)(2) (5) for the solid-phase synthesis of L-OMT containing peptides as modulators of cellular signal transduction. Additionally included is the preparation of N-alpha-Fmoc-L-OMT-O,O-(n-butyl)(2) (6) for the direct solid-phase synthesis of OMT-peptide diester prodrugs for use in cell-based studies.

  DOI：

  10.1016/0040-4039(95)00890-o
• 作为产物：
  描述：

  丙二酸二丁酯 在 对甲苯磺酰叠氮 、 三乙胺 作用下， 以 苯 为溶剂， 反应 168.0h， 生成 dibutyl diazomalonate
  参考文献：
  名称：

  L-O-(2-malonyl)tyrosine (L-OMT) a new phosphotyrosyl mimic suitably protected for solid-phase synthesis of signal transduction inhibitory peptides

  摘要：

  A new phosphotyrosyl (pTyr) mimic L-O-(2-malonyl)tyrosine (L-OMT, 4) utilizes a malonyl structure in place of the parent phosphate group. This compound is stable to protein-tyrosine phosphatases and has advantages over phosphonate-based pTyr mimics in that protection of the malonyl group as its diester allows passage of the OMT across cell membranes, with subsequent esterase-mediated liberation of the free diacid once inside cells. Herein is reported the synthesis of N-alpha-Fmoc-L-OMT-O,O-(tert-butyl)(2) (5) for the solid-phase synthesis of L-OMT containing peptides as modulators of cellular signal transduction. Additionally included is the preparation of N-alpha-Fmoc-L-OMT-O,O-(n-butyl)(2) (6) for the direct solid-phase synthesis of OMT-peptide diester prodrugs for use in cell-based studies.

  DOI：

  10.1016/0040-4039(95)00890-o

文献信息

• Reversal of regioselectivity in reactions of donor–acceptor cyclopropanes with electrophilic olefins
  作者：Joanna Turkowska、Jakub Durka、Michał Ociepa、Dorota Gryko

  DOI：10.1039/d1cc05330b

  日期：——

  Reactivity of donor–acceptor cyclopropanes towards nucleophiles and electrophiles is determined by the specific philicity of the carbon atoms originating from the strong polarization of the central C–C bond. Herein, we report that vitamin B12 catalysis enables the transformation of an initially electrophilic center into a nucleophilic radical that reacts with SOMOphiles. This radical-based strategy

  供体 - 受体环丙烷对亲核试剂和亲电试剂的反应性由源自中心 C-C 键的强极化的碳原子的特定亲水性决定。在此，我们报道维生素 B 12催化能够将最初的亲电中心转变为与 SOMophiles 反应的亲核自由基。这种基于自由基的策略逆转了标准的区域选择性，从而补充了经典方法。
• Antimony-based “forcing knoevenagel” methodology for the conversion of ketones into alkylidenemalonates
  作者：Anthony P. Davis、Khadga M. Bhattarai

  DOI：10.1016/0040-4020(95)00418-8

  日期：1995.7

  The Knoevenagel condensation between ketones and malonate esters is often unattainable using conventional methodology. Antimony-based alternatives, arising from the studies of Zhang and co-workers, have been assessed in the context of “cholaphane” synthesis. New conditions have been established which allow the conversion of highly functionalised steroidal ketones into alkylidenemalonates by treatment

  酮和丙二酸酯之间的Knoevenagel缩合通常无法通过常规方法获得。张和同事的研究产生了基于锑的替代品，已在“胆碱”合成的背景下进行了评估。已经建立了新的条件，该条件允许通过用二溴丙二酸酯和三丁基锡比汀处理将高度官能化的甾族酮转化为亚甲基丙二酸酯。
• A C–H Activation-Based Strategy for <i>N</i>-Amino Azaheterocycle Synthesis
  作者：Pengfei Shi、Lili Wang、Shan Guo、Kehao Chen、Jie Wang、Jin Zhu

  DOI：10.1021/acs.orglett.7b02066

  日期：2017.8.18

  A C–H activation-based strategy has been developed for the synthesis of N-amino azaheterocycles. Rh(III)-catalyzed coupling of N-Boc hydrazones/N-Boc hydrazines with diazodiesters/diazoketoesters provides convenient access to synthetically and medicinally important compounds, N-amino isoquinolin-3-ones and N-amino indoles, by harnessing N-tert-butyloxycarbonyl (N-Boc) cleavage as an adaptable reactivity

  已经开发出基于AC–H活化的策略来合成N-氨基氮杂杂环。铑（III）催化的的耦合Ñ -Boc腙/ Ñ -Boc肼与diazodiesters / diazoketoesters提供了合成和医药上重要的化合物，方便地访问ñ -氨基异喹啉-3-酮和Ñ -氨基吲哚，通过利用Ñ -叔丁氧羰基（N -Boc）裂解作为一种适应性反应模式在不同的合成方案中。
• Rh(III)-Catalyzed C–H Cyclization of Arylnitrones with Diazo Compounds: Access to <i>N</i>-Hydroxyindolines
  作者：Ramesh B. Dateer、Sukbok Chang

  DOI：10.1021/acs.orglett.5b03273

  日期：2016.1.4

  We have developed the Cp*Rh(III)-catalyzed cyclization reaction of arylnitrones with diazo compounds to obtain N-hydroxyindoline products under mild conditions. The substrate scope and functional group compatibility were examined with the demonstration of synthetic utility.
• L-O-(2-malonyl)tyrosine (L-OMT) a new phosphotyrosyl mimic suitably protected for solid-phase synthesis of signal transduction inhibitory peptides
  作者：Bin Ye、Terrence R Burke

  DOI：10.1016/0040-4039(95)00890-o

  日期：1995.7

  A new phosphotyrosyl (pTyr) mimic L-O-(2-malonyl)tyrosine (L-OMT, 4) utilizes a malonyl structure in place of the parent phosphate group. This compound is stable to protein-tyrosine phosphatases and has advantages over phosphonate-based pTyr mimics in that protection of the malonyl group as its diester allows passage of the OMT across cell membranes, with subsequent esterase-mediated liberation of the free diacid once inside cells. Herein is reported the synthesis of N-alpha-Fmoc-L-OMT-O,O-(tert-butyl)(2) (5) for the solid-phase synthesis of L-OMT containing peptides as modulators of cellular signal transduction. Additionally included is the preparation of N-alpha-Fmoc-L-OMT-O,O-(n-butyl)(2) (6) for the direct solid-phase synthesis of OMT-peptide diester prodrugs for use in cell-based studies.