dimethyl 3-[(dimethylphenylsilyl)methyl]-4-methyl-cyclopentane-1,1-dicarboxylate

• 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: dimethyl 3-[(dimethylphenylsilyl)methyl]-4-methyl-cyclopentane-1,1-dicarboxylate
• 英文别名: dimethyl (3S,4S)-3-[[dimethyl(phenyl)silyl]methyl]-4-methylcyclopentane-1,1-dicarboxylate
• 化学式: C₁₉H₂₈O₄Si
• 分子量: 348.514
• InChiKey: OJKLNRBDWYACTF-LSDHHAIUSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.98
• 重原子数：
  24
• 可旋转键数：
  7
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.58
• 拓扑面积：
  52.6
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  dimethyl 3-[(dimethylphenylsilyl)methyl]-4-methyl-cyclopentane-1,1-dicarboxylate 在 过氧乙酸 、 三甲基氯硅烷 、 mercury(II) diacetate 、 sodium iodide 作用下， 以 溶剂黄146 、 乙腈 为溶剂， 反应 14.0h， 生成 dimethyl trans-3,4-dimethylcyclopentane-1,1-dicarboxylate
  参考文献：
  名称：

  Cyclization/Hydrosilylation of Functionalized Dienes Catalyzed by a Cationic Palladium Phenanthroline Complex

  摘要：

  Mixtures of(phen)PdMe2 (2a) and HBAr'(4) (3a) or (phen)PdMe(Cl) (2b) and NaBAr'(4) (3b) [phen = 1, 10-phenanthroline; Ar' = 3,5-C6H3(CF3)(2)] catalyzed the cyclization/hydrosilylation of functionalized 1,6-dienes to form silylated cyclopentanes in good yield and with excellent trans selectivity about the newly formed C-C bond (typically >50:1). A range of tertiary hydrosilanes were employed in the procedure although unhindered trialkylsilanes provided the most consistent results. The protocol tolerated a range of polar functionality including esters, ethers, amides, sulfones, and cyano groups. 4,4-Disubstitution on the diene backbone promoted cyclization, and a homoallylic ester, ketone, or ether directing group was required for efficient cyclization. The procedure tolerated dienes which possessed a single trans-substituted olefin and also tolerated allylic substitution. These substituted dienes underwent cyclization/hydrosilylation to form carbocycles resulting from transfer of the silyl group to the less hindered olefin. Mixtures of 2a and 3a also catalyzed the cyclization/hydrosilylation of functionalized 1,7-dienes to form silylated cyclohexane derivatives. Cyclization/hydrosilylation of 1,7-dienes was typically slower, less stereoselective, and more sensitive to substitution than was cyclization of 1,6-dienes.

  DOI：

  10.1021/jo9913006
• 作为产物：
  描述：

  苯基二甲基氯硅烷 在 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile 作用下， 以 正己烷 为溶剂， 反应 16.0h， 生成 dimethyl 3-[(dimethylphenylsilyl)methyl]-4-methyl-cyclopentane-1,1-dicarboxylate
  参考文献：
  名称：

  Radical Transfer Hydrosilylation/Cyclization Using Silylated Cyclohexadienes

  摘要：

  [GRAPHICS]A new method for mild metal free hydrosilylation is described, Silylated cyclohexadienes are used as radical transfer hydrosilylating reagents for various double and triple bonds, A trialkylsilane is transferred from a cyclohexadiene moiety to an alkene. The hydrosilylation can be combined with a C-C bond formation as shown for the preparation of silylated cycloalkanes from the corresponding dienes.

  DOI：

  10.1021/ol016160c

文献信息

• Enantioselective Diene Cyclization/Hydrosilylation Catalyzed by Optically Active Palladium Bisoxazoline and Pyridine−Oxazoline Complexes
  作者：Nicholas S. Perch、Tao Pei、Ross A. Widenhoefer

  DOI：10.1021/jo0003192

  日期：2000.6.1

  palladium pyridine-oxazoline complex (N-N)Pd(Me)Cl ¿N-N = (R)-(+)-4-isopropyl-2-(2-pyridinyl)-2-oxazoline (R-5b) and NaBAr(4) (5 mol %) catalyzed the asymmetric cyclization/hydrosilylation of 2 and triethylsilane at -32 degrees C for 24 h to form carbocycle S,S-3 in 82% yield (>95% de, 87% ee) as the exclusive product. Asymmetric diene cyclization catalyzed by complex R-5b was compatible with a range

  （NN）Pd（Me）Cl（NN =（S，S）-4,4'-di苄基-4,5,4'，5'-四氢-2,2'-双恶唑啉的1：1混合物，S-4a）和NaBAr（4）？Ar = 3，5-C（6）H（3）（CF（3））（2）（5 mol％）催化二烯丙基二丙二酸二甲酯的不对称环化/氢化硅烷化反应（2 ）和三乙基硅烷在-30摄氏度下反应48小时，以形成甲硅烷基化的碳环（S，S）-trans-1，1-二苯甲氧基-4-甲基-3-¿（三乙基甲硅烷基）甲基环戊烷（ S，S-3）（95％de，72％ee）和3，4-二甲基环戊烷-1，1-二羧酸二甲酯（S，S-6）的合并产率为64％。相比之下，钯吡啶-恶唑啉络合物（NN）Pd（Me）Cl = NN =（R）-（+）-4-异丙基-2-（2-吡啶基）-2-恶唑啉（ R-5b）和NaBAr（4）（5 mol％）在-32摄氏度下催化2和三乙基硅烷的不对称环化/氢化硅烷化24小时
• Tandem Cyclization/Hydrosilylation of Functionalized 1,6-Dienes Catalyzed by a Cationic Palladium Complex
  作者：Ross A. Widenhoefer、Michael A. DeCarli

  DOI：10.1021/ja980242n

  日期：1998.4.1
• Cyclization/Hydrosilylation of Functionalized Dienes Catalyzed by a Cationic Palladium Phenanthroline Complex
  作者：Ross A. Widenhoefer、Carmine N. Stengone

  DOI：10.1021/jo9913006

  日期：1999.11.1

  Mixtures of(phen)PdMe2 (2a) and HBAr'(4) (3a) or (phen)PdMe(Cl) (2b) and NaBAr'(4) (3b) [phen = 1, 10-phenanthroline; Ar' = 3,5-C6H3(CF3)(2)] catalyzed the cyclization/hydrosilylation of functionalized 1,6-dienes to form silylated cyclopentanes in good yield and with excellent trans selectivity about the newly formed C-C bond (typically >50:1). A range of tertiary hydrosilanes were employed in the procedure although unhindered trialkylsilanes provided the most consistent results. The protocol tolerated a range of polar functionality including esters, ethers, amides, sulfones, and cyano groups. 4,4-Disubstitution on the diene backbone promoted cyclization, and a homoallylic ester, ketone, or ether directing group was required for efficient cyclization. The procedure tolerated dienes which possessed a single trans-substituted olefin and also tolerated allylic substitution. These substituted dienes underwent cyclization/hydrosilylation to form carbocycles resulting from transfer of the silyl group to the less hindered olefin. Mixtures of 2a and 3a also catalyzed the cyclization/hydrosilylation of functionalized 1,7-dienes to form silylated cyclohexane derivatives. Cyclization/hydrosilylation of 1,7-dienes was typically slower, less stereoselective, and more sensitive to substitution than was cyclization of 1,6-dienes.
• Radical Transfer Hydrosilylation/Cyclization Using Silylated Cyclohexadienes
  作者：Stephan Amrein、Andreas Timmermann、Armido Studer

  DOI：10.1021/ol016160c

  日期：2001.7.1

  [GRAPHICS]A new method for mild metal free hydrosilylation is described, Silylated cyclohexadienes are used as radical transfer hydrosilylating reagents for various double and triple bonds, A trialkylsilane is transferred from a cyclohexadiene moiety to an alkene. The hydrosilylation can be combined with a C-C bond formation as shown for the preparation of silylated cycloalkanes from the corresponding dienes.