(5-Cyclopropyl-penta-1,3-diynyl)-trimethyl-silane | 909716-37-6

• 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: (5-Cyclopropyl-penta-1,3-diynyl)-trimethyl-silane
• 英文别名: (5-Cyclopropylpenta-1,3-diyn-1-yl)(trimethyl)silane；5-cyclopropylpenta-1,3-diynyl(trimethyl)silane
• CAS: 909716-37-6
• 化学式: C₁₁H₁₆Si
• 分子量: 176.334
• InChiKey: CTVYCNMWVDVQNX-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.67
• 重原子数：
  12
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.64
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  0

反应信息

• 作为反应物：
  描述：

  (5-Cyclopropyl-penta-1,3-diynyl)-trimethyl-silane 、 乙醛酸乙酯 在 bis(1,5-cyclooctadiene)rhodium(I) trifluoromethanesulfonate 、 氢气 、 (S)-(-)-5,5-二氯-6,6-二甲氧基-2,2-双(二苯基磷酸)-1,1-联苯基 作用下， 以 1,2-二氯乙烷 为溶剂， 40.0 ℃ 、100.0 kPa 条件下， 生成 (Z)-(R)-7-Cyclopropyl-2-hydroxy-3-trimethylsilanyl-hept-3-en-5-ynoic acid ethyl ester 、 (Z)-(S)-7-Cyclopropyl-2-hydroxy-3-trimethylsilanyl-hept-3-en-5-ynoic acid ethyl ester
  参考文献：
  名称：

  α-Hydroxy Esters via Enantioselective Hydrogen-Mediated C−C Coupling:  Regiocontrolled Reactions of Silyl-Substituted 1,3-Diynes

  摘要：

  Catalytic hydrogenation of ethyl glyoxalate in the presence of 1,3-diynes 4a-9a using chirally modified rhodium catalysts enables formation of alpha-hydroxy esters 4c-9c in highly optically enriched form. Notably, for such trialkylsilyl-substituted 1,3-diynes, C-C coupling occurs exclusively at the carbon atom bearing silicon. pi-Back-bonding from low valent rhodium as described by the Dewar-Chatt-Duncanson model appears to direct the regiochemistry of C-C coupling, as corroborated by calculations of the diyne LUMO coefficients.

  DOI：

  10.1021/ol061485k

文献信息

• α-Hydroxy Esters via Enantioselective Hydrogen-Mediated C−C Coupling:  Regiocontrolled Reactions of Silyl-Substituted 1,3-Diynes
  作者：Chang-Woo Cho、Michael J. Krische

  DOI：10.1021/ol061485k

  日期：2006.8.1

  Catalytic hydrogenation of ethyl glyoxalate in the presence of 1,3-diynes 4a-9a using chirally modified rhodium catalysts enables formation of alpha-hydroxy esters 4c-9c in highly optically enriched form. Notably, for such trialkylsilyl-substituted 1,3-diynes, C-C coupling occurs exclusively at the carbon atom bearing silicon. pi-Back-bonding from low valent rhodium as described by the Dewar-Chatt-Duncanson model appears to direct the regiochemistry of C-C coupling, as corroborated by calculations of the diyne LUMO coefficients.