(E)-tert-butyldimethyl((3-methylhex-2-en-4-yn-1-yl)oxy)silane | 154547-38-3

• 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: (E)-tert-butyldimethyl((3-methylhex-2-en-4-yn-1-yl)oxy)silane
• 英文别名: tert-butyl-dimethyl-[(E)-3-methylhex-2-en-4-ynoxy]silane
• CAS: 154547-38-3
• 化学式: C₁₃H₂₄OSi
• 分子量: 224.418
• InChiKey: FHPHKFXBORRYFP-ZRDIBKRKSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.98
• 重原子数：
  15
• 可旋转键数：
  5
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.69
• 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：

  (E)-tert-butyldimethyl((3-methylhex-2-en-4-yn-1-yl)oxy)silane 在 manganese(IV) oxide 、 铂(0)-1,3-二乙烯-1,1,3,3-四甲基二硅氧烷 、 三叔丁基膦 、 四丁基氟化铵 、 sodium carbonate 作用下， 以 四氢呋喃 、 5,5-dimethyl-1,3-cyclohexadiene 、 乙醚 、 甲苯 为溶剂， 反应 10.0h， 生成 all-trans-11-methylretinal
  参考文献：
  名称：

  C11到C14甲基转移的全反式视网膜类似物的合成及其对人醛基酮还原酶的活性。

  摘要：

  人醛基酮还原酶（AKR）是参与将所有反式-视网膜还原为全反式-视黄醇（维生素A）的酶，因此有助于控制生物体中类维生素A的水平。一系列C11-C14甲基转移（相对于天然C13-甲基）全反式的构效关系研究已经报道了-视网膜类似物作为AKR的假定底物。这些类维生素A的合成基于戊烯骨架的C10–C11单键的形成，分别从Stille–Kosugi–Migita和Hiyama–Denmark交叉偶联反应开始，从三苯基碘化物以及相应的二苯基锡烷和二苯基硅烷开始。 。由于这些试剂的不同之处在于二烯基有机金属片段上甲基的位置和存在，因此该研究还提供了对不同位置异构体进行交叉偶联的能力以及这些过程对位阻的敏感性的见解。所得的C11至C14甲基转移的全反式尽管已注意到底物特异性的相关差异，但在用AKR1B1和AKR1B10酶进行测试时，发现视网膜类似物是活性底物。对于AKR1B1，所有类似物均比母体全反式视网膜表现出更高的催化效率（k

  DOI：

  10.1039/d0ob01084g
• 作为产物：
  描述：

  (E)-3-甲基戊-2-烯-4-炔-1-醇 在 咪唑 、 4-二甲氨基吡啶 、 正丁基锂 作用下， 以 四氢呋喃 、 正己烷 、 二氯甲烷 为溶剂， 反应 13.0h， 生成 (E)-tert-butyldimethyl((3-methylhex-2-en-4-yn-1-yl)oxy)silane
  参考文献：
  名称：

  Enantioselective Synthesis of Carbohydrate Precursors via 1,2:2,3-Bis-Epoxide Intermediates

  摘要：

  Bis-epoxidation of the DPS-substituted allenylcarbinyl acetates 9, 13, 19, 22, and 30 afforded the enones 10, 36, 20, 23, and 31, respectively, in 80-90 % yield with excellent stereoselectivity. Treatment with DBU effected C to O DPS transfer leading to the methyl-branched hexose precursors, enones 11, 37, 21, and 24. The higher homologue 33 gave the branched 7-deoxyheptose precursor 33. Reduction of enones 11, 37, and 33 with NaBH4-CeCl3 yielded the alpha-(S) alcohols 12, 38, and 35 in high yield. Alcohol 38 was converted to the 1-deoxy-4-methylpyranose tetraacetate 48 by epoxidation, base treatment, desilylation, and acetylation. An acyclic analogue of 48, acetonide 53, could be prepared from epoxide 39 by treatment with PhSH and NaOH, followed by silyl ether cleavage, acetonide formation, and Pummerer rearrangement-reduction. On the other hand, hydroxylation of alcohol 38 with OsO4-NMO led to the selectively protected branched hexitol 59, with high diastereoselectivity. The allylic alcohol benzoate 63 was likewise converted to diol 64.

  DOI：

  10.1021/jo00085a038

文献信息

• Enantioselective Synthesis of Carbohydrate Precursors via 1,2:2,3-Bis-Epoxide Intermediates
  作者：James A. Marshall、Ying Tang

  DOI：10.1021/jo00085a038

  日期：1994.3

  Bis-epoxidation of the DPS-substituted allenylcarbinyl acetates 9, 13, 19, 22, and 30 afforded the enones 10, 36, 20, 23, and 31, respectively, in 80-90 % yield with excellent stereoselectivity. Treatment with DBU effected C to O DPS transfer leading to the methyl-branched hexose precursors, enones 11, 37, 21, and 24. The higher homologue 33 gave the branched 7-deoxyheptose precursor 33. Reduction of enones 11, 37, and 33 with NaBH4-CeCl3 yielded the alpha-(S) alcohols 12, 38, and 35 in high yield. Alcohol 38 was converted to the 1-deoxy-4-methylpyranose tetraacetate 48 by epoxidation, base treatment, desilylation, and acetylation. An acyclic analogue of 48, acetonide 53, could be prepared from epoxide 39 by treatment with PhSH and NaOH, followed by silyl ether cleavage, acetonide formation, and Pummerer rearrangement-reduction. On the other hand, hydroxylation of alcohol 38 with OsO4-NMO led to the selectively protected branched hexitol 59, with high diastereoselectivity. The allylic alcohol benzoate 63 was likewise converted to diol 64.
• Synthesis of C11-to-C14 methyl-shifted all-<i>trans</i>-retinal analogues and their activities on human aldo-keto reductases
  作者：Aurea Rivas、Raquel Pequerul、Vito Barracco、Marta Domínguez、Susana López、Rafael Jiménez、Xavier Parés、Rosana Alvarez、Jaume Farrés、Angel R. de Lera

  DOI：10.1039/d0ob01084g

  日期：——

  The synthesis of these retinoids was based on the formation of a C10–C11 single bond of the pentaene skeleton starting from a trienyl iodide and the corresponding dienylstannanes and dienylsilanes, using the Stille–Kosugi–Migita and Hiyama–Denmark cross-coupling reactions, respectively. Since these reagents differ by the location and presence of methyl groups at the dienylorganometallic fragment, the

  人醛基酮还原酶（AKR）是参与将所有反式-视网膜还原为全反式-视黄醇（维生素A）的酶，因此有助于控制生物体中类维生素A的水平。一系列C11-C14甲基转移（相对于天然C13-甲基）全反式的构效关系研究已经报道了-视网膜类似物作为AKR的假定底物。这些类维生素A的合成基于戊烯骨架的C10–C11单键的形成，分别从Stille–Kosugi–Migita和Hiyama–Denmark交叉偶联反应开始，从三苯基碘化物以及相应的二苯基锡烷和二苯基硅烷开始。 。由于这些试剂的不同之处在于二烯基有机金属片段上甲基的位置和存在，因此该研究还提供了对不同位置异构体进行交叉偶联的能力以及这些过程对位阻的敏感性的见解。所得的C11至C14甲基转移的全反式尽管已注意到底物特异性的相关差异，但在用AKR1B1和AKR1B10酶进行测试时，发现视网膜类似物是活性底物。对于AKR1B1，所有类似物均比母体全反式视网膜表现出更高的催化效率（k
• Radical Hydrostannylation, Pd(0)-Catalyzed Hydrostannylation, Stannylcupration of Propargyl Alcohols and Enynols:  Regio- and Stereoselectivities
  作者：Jean-François Betzer、Francette Delaloge、Benoît Muller、Ange Pancrazi、Joëlle Prunet

  DOI：10.1021/jo9710339

  日期：1997.10.1

  Different enynols and propargyl derivatives were sumitted to radical hydrostannylation (Bu3SnH/AIBN), Pd(0)-catalyzed hydrostannylation [Bu3SnH/Pd(0)], and stannylcupration [Bu3Sn(R)CuCNLi2] conditions. Except for the radical stannylation reaction, high regio-and stereoselective formation of vinyl-and dienylstannanes are obtained. Results are tentatively explained in terms of steric Interactions between the alkyne or enyne substituents and the palladium or cuprate moieties in the different reaction intermediates.