(3R,4E)-methyl 3-(t-butyldimethylsilyloxy)-2,2,4-trimethylhept-4-en-6-ynoate | 1404069-81-3

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 脂肪酰基
• 英文名称: (3R,4E)-methyl 3-(t-butyldimethylsilyloxy)-2,2,4-trimethylhept-4-en-6-ynoate
• 英文别名: methyl (E,3R)-3-[tert-butyl(dimethyl)silyl]oxy-2,2,4-trimethylhept-4-en-6-ynoate
• CAS: 1404069-81-3
• 化学式: C₁₇H₃₀O₃Si
• 分子量: 310.509
• InChiKey: VQQVMXJCPWEATI-XTZCOPOCSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.16
• 重原子数：
  21
• 可旋转键数：
  7
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.71
• 拓扑面积：
  35.5
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  (3R,4E)-methyl 3-(t-butyldimethylsilyloxy)-2,2,4-trimethylhept-4-en-6-ynoate 在 4-二甲氨基吡啶 、 氢氟酸 、 N,N'-二环己基碳二亚胺 作用下， 以 二氯甲烷 、 水 、 乙腈 为溶剂， 反应 24.0h， 生成 methyl (3R,E)-2,2,4-trimethyl-3-((3,3,3-trifluoro-2-methoxy-2-phenylpropanoyl)oxy)hept-4-en-6-ynoate
  参考文献：
  名称：

  Asymmetric Total Synthesis of (+)-Inthomycin C via O-Directed Free Radical Alkyne Hydrostannation with Ph₃SnH and Catalytic Et₃B: Reinstatement of the Zeeck–Taylor (3R)-Structure for (+)-Inthomycin C

  摘要：

  A new pathway to (+)-inthomycin C is reported that exploits an O-directed free radical hydrostannation reaction on (-)-12 and a Stille cross-coupling as key steps. Significantly, the latter process was effected on 19 where a gauche-pentane repulsive interaction could interfere. Our stereochemical studies on the alkynol (-)-12 and the enyne (+)-7 confirm that Ryu and Hatakeyama's (3S)-stereochemical revision of (+)-inthomycin C is invalid and that Zeeck and Taylor's original (3R)-stereostructure for (+)-inthomycin C is correct.

  DOI：

  10.1021/ol5000499
• 作为产物：
  描述：

  羟基三甲基乙酸甲酯 在 咪唑 、 2,6-二甲基吡啶 、 sodium periodate 、 N-碘代丁二酰亚胺 、 copper(l) iodide 、 四(三苯基膦)钯 、 三乙基硼 、 AD-mix-β 、 N-甲基麻黄碱 、 potassium tert-butylate 、 碘 、 三氧化硫吡啶 、 zinc trifluoromethanesulfonate 、 二甲基亚砜 、 1,8-二氮杂双环[5.4.0]十一碳-7-烯 、 三乙胺 、 三苯基膦 、 cesium fluoride 、 2,3-二氯-5,6-二氰基-1,4-苯醌 作用下， 以 四氢呋喃 、 正己烷 、 二氯甲烷 、 水 、 N,N-二甲基甲酰胺 、 甲苯 、 叔丁醇 为溶剂， 反应 142.41h， 生成 (3R,4E)-methyl 3-(t-butyldimethylsilyloxy)-2,2,4-trimethylhept-4-en-6-ynoate
  参考文献：
  名称：

  Asymmetric Total Synthesis of (+)-Inthomycin C via O-Directed Free Radical Alkyne Hydrostannation with Ph₃SnH and Catalytic Et₃B: Reinstatement of the Zeeck–Taylor (3R)-Structure for (+)-Inthomycin C

  摘要：

  A new pathway to (+)-inthomycin C is reported that exploits an O-directed free radical hydrostannation reaction on (-)-12 and a Stille cross-coupling as key steps. Significantly, the latter process was effected on 19 where a gauche-pentane repulsive interaction could interfere. Our stereochemical studies on the alkynol (-)-12 and the enyne (+)-7 confirm that Ryu and Hatakeyama's (3S)-stereochemical revision of (+)-inthomycin C is invalid and that Zeeck and Taylor's original (3R)-stereostructure for (+)-inthomycin C is correct.

  DOI：

  10.1021/ol5000499

文献信息

• Organocatalytic asymmetric syntheses of inthomycins A, B and C
  作者：Madoka Yoshino、Kohei Eto、Keisuke Takahashi、Jun Ishihara、Susumi Hatakeyama

  DOI：10.1039/c2ob26084k

  日期：——

  The total syntheses of (+)-inthomycin A, (+)-inthomycin B and (−)-inthomycin C, the oxazole-triene antibiotics isolated from Streptomyces sp., have been accomplished via the highly enantio- and stereoselective construction of the C1–C7 (iododienyl)aldol units by taking advantage of a Cinchona alkaloid-catalyzed asymmetric β-lactone synthesis and their isomerisation-free Stille coupling with (E)-5-

  分离自链霉菌属的恶唑三烯类抗生素-（+）-ththomycin A，（+）-ththomycin B和（-）-ththomycin C的总合成是通过C1的高度对映体和立体选择性构建而完成的利用金鸡纳生物碱催化的不对称β-内酯合成及其无异构化的Stille偶联，可合成–C7（碘二烯基）醛醇单元（E）-5-（3-（三丁基锡烷基）烯丙基）恶唑。
• Asymmetric Total Synthesis of (+)-Inthomycin C via O-Directed Free Radical Alkyne Hydrostannation with Ph₃SnH and Catalytic Et₃B: Reinstatement of the Zeeck–Taylor (3<i>R</i>)-Structure for (+)-Inthomycin C
  作者：Karl J. Hale、Milosz Grabski、Soraya Manaviazar、Maciej Maczka

  DOI：10.1021/ol5000499

  日期：2014.2.21

  A new pathway to (+)-inthomycin C is reported that exploits an O-directed free radical hydrostannation reaction on (-)-12 and a Stille cross-coupling as key steps. Significantly, the latter process was effected on 19 where a gauche-pentane repulsive interaction could interfere. Our stereochemical studies on the alkynol (-)-12 and the enyne (+)-7 confirm that Ryu and Hatakeyama's (3S)-stereochemical revision of (+)-inthomycin C is invalid and that Zeeck and Taylor's original (3R)-stereostructure for (+)-inthomycin C is correct.