(+/-)-1-(tert-butyldimethylsilyloxymethyl)-2-methylenecyclopropane | 457646-63-8

• 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: (+/-)-1-(tert-butyldimethylsilyloxymethyl)-2-methylenecyclopropane
• 英文别名: Tert-butyl-dimethyl-[(2-methylidenecyclopropyl)methoxy]silane
• CAS: 457646-63-8
• 化学式: C₁₁H₂₂OSi
• 分子量: 198.381
• InChiKey: AZEYWIBHHMDYJE-UHFFFAOYSA-N

物化性质

• 沸点：
  197.6±9.0 °C(predicted)
• 密度：
  0.86±0.1 g/cm3(Temp: 20 °C; Press: 760 Torr)(predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.58
• 重原子数：
  13
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.82
• 拓扑面积：
  9.2
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  (+/-)-1-(tert-butyldimethylsilyloxymethyl)-2-methylenecyclopropane 在 dirhodium tetraacetate 、 sodium hydroxide 、 sodium azide 、 jones' reagent 、 18-冠醚-6 、 四丁基氟化铵 、 potassium carbonate 作用下， 以 四氢呋喃 、 乙醇 、 二氯甲烷 、 水 、 丙酮 为溶剂， 反应 55.0h， 生成 (+/-)-distal-1-aminospiro[2.2]pentane-1,4-dicarboxylic acid
  参考文献：
  名称：

  Spiro[2.2]pentane as a Dissymmetric Scaffold for Conformationally Constrained Analogues of Glutamic Acid:  Focus on Racemic 1-Aminospiro[2.2]pentyl-1,4-dicarboxylic Acids

  摘要：

  In search for novel conformationally constrained analogues of L-glutamic acid, a diastereodivergent synthesis of the four 1-aminospiro[2.2]pentyl-1,4-dicarboxylic acid racernic pairs is reported along with their stereochemical assignment, conformational analysis, and preliminary biological evaluation as potential glutamate (ionotropic and metabotropic) ligands.

  DOI：

  10.1021/jo020138v
• 作为产物：
  描述：

  (2-亚甲基环丙基)甲醇 、 叔丁基二甲基氯硅烷 在 4-二甲氨基吡啶 作用下， 以 二氯甲烷 为溶剂， 以55%的产率得到(+/-)-1-(tert-butyldimethylsilyloxymethyl)-2-methylenecyclopropane
  参考文献：
  名称：

  Spiro[2.2]pentane as a Dissymmetric Scaffold for Conformationally Constrained Analogues of Glutamic Acid:  Focus on Racemic 1-Aminospiro[2.2]pentyl-1,4-dicarboxylic Acids

  摘要：

  In search for novel conformationally constrained analogues of L-glutamic acid, a diastereodivergent synthesis of the four 1-aminospiro[2.2]pentyl-1,4-dicarboxylic acid racernic pairs is reported along with their stereochemical assignment, conformational analysis, and preliminary biological evaluation as potential glutamate (ionotropic and metabotropic) ligands.

  DOI：

  10.1021/jo020138v

文献信息

• Site- and Regioselective Silaborative C–C Cleavage of 1-Alkyl-2-Methylenecyclopropanes Using a Platinum Catalyst with a Sterically Demanding Silylboronic Ester
  作者：Toshimichi Ohmura、Hiroki Taniguchi、Michinori Suginome

  DOI：10.1021/acscatal.5b00513

  日期：2015.5.1

  presence of a phosphine-free platinum catalyst, giving 3-substituted 2-boryl-4-silyl-1-butenes through selective cleavage of the less hindered proximal C–C bond of the cyclopropane ring. The steric bulk of the silyl group of the silylboronic esters was critical for efficient formation of the silaboration products, and i-PrPh2Si–B(pin) was developed as a silylboronic ester of choice.

  1-烷基-2-亚甲基环丙烷在无膦的铂催化剂存在下，在温和条件下与甲硅烷基硼酸酯反应，通过选择性裂解受阻较弱的近端C–生成3-取代的2-硼基-4-甲硅烷基-1-丁烯环丙烷环的C键。甲硅烷基硼酸酯的甲硅烷基的空间体积对于有效形成甲硅烷基化产物至关重要，因此开发了i -PrPh 2 Si–B（pin）作为选择的甲硅烷基硼酸酯。
• Methylenecyclopropanes in [4 + 1] Cycloaddition with Enones
  作者：Tasuku Inami、Saori Sako、Takuya Kurahashi、Seijiro Matsubara

  DOI：10.1021/ol201540b

  日期：2011.8.5

  A nickel-catalyzed [4 + 1] cycloaddition of enones with methylenecyclopropanes leading to dihydrofurans was developed. The reaction outcome is attributed to the transformation of methlenecyclopropane, which is incorporated Into a five-membered ring as a one-carbon fragment.
• Kinetic Resolution of Racemic 1-Alkyl-2-methylenecyclopropanes via Palladium-Catalyzed Silaborative C−C Cleavage
  作者：Toshimichi Ohmura、Hiroki Taniguchi、Michinori Suginome

  DOI：10.1021/ol900829c

  日期：2009.7.2

  Kinetic resolution of racemic 1-alkyl-2-methylenecyclopropanes via silaborative C-C cleavage was efficiently catalyzed by a palladium complex bearing a chiral phosphoramidite, affording 2-boryl-3-silylmethyl-1-alkenes as major products with up to 92% ee. Enantioenrichment through parallel kinetic resolution, where the slower reacting enantiomer was converted to the constitutional isomer of the major product, may be involved as the crucial stereodiscriminating step.