3-triisopropylsiloxy-1,3-pentadiene | 183114-70-7

• 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: 3-triisopropylsiloxy-1,3-pentadiene
• 英文别名: [(3Z)-penta-1,3-dien-3-yl]oxy-tri(propan-2-yl)silane
• CAS: 183114-70-7
• 化学式: C₁₄H₂₈OSi
• 分子量: 240.461
• InChiKey: VQXCMVSNNBXFKV-UVTDQMKNSA-N

物化性质

• 沸点：
  236.6±8.0 °C(predicted)
• 密度：
  0.825±0.06 g/cm3(Temp: 20 °C; Press: 760 Torr)(predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  5.27
• 重原子数：
  16
• 可旋转键数：
  6
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.71
• 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：

  3-triisopropylsiloxy-1,3-pentadiene 在 镍 chiral oxazaborolidinium*Tf₂N^(1-) derivative 、 氢气 作用下， 以 二氯甲烷 、 苯 为溶剂， -78.0~20.0 ℃ 、101.33 kPa 条件下， 反应 2.5h， 生成 (+)-(4aR,5S,8aS)-2,3,4a,5,8,8a-hexahydro-8-(triisopropylsilyl)oxy-6-methylnaphthalene-1,4-dione
  参考文献：
  名称：

  Application of Chiral Cationic Catalysts to Several Classical Syntheses of Racemic Natural Products Transforms Them into Highly Enantioselective Pathways

  摘要：

  This paper describes the application of chiral oxazaborolidinium cations of type 2 to various enantioselective Diels-Alder reactions that have served as early key steps for the syntheses of complex natural products. In the original syntheses these Diels-Alder reactions produced racemic adducts and led to racemic target molecules unless a separation of enantiomers by classical resolution was employed. By use of chiral catalysts of type 2, chiral products were obtained directly from Diels-Alder reactions of achiral components in excellent yield and enantioselectivity and with the mechanistically predicted absolute configuration. As a result, a number of classical syntheses could be converted to enantioselective versions, including (1) cortisone/cortisol (Merck/Sarett), (2) dendrobine (Kende), (3) vitamin B-12 (Eschenmoser), (4) myrocin C (Chu-Moyer/Danishefsky), (5) coriolin and hirsutene (Mehta), (6) dendrobatid 251F (Aube), (7) silphinene (Ito), and (8) nicandrenone core (Stoltz/Corey).

  DOI：

  10.1021/ja046154m
• 作为产物：
  描述：

  三异丙基硅基三氟甲磺酸酯 、 乙烯基乙醚 在 双(三甲基硅烷基)氨基钾 作用下， 以 四氢呋喃 为溶剂， 以84%的产率得到3-triisopropylsiloxy-1,3-pentadiene
  参考文献：
  名称：

  Stereoselective Synthesis of Dihydropyran-4-ones via a Formal Hetero Diels−Alder Reaction and Ceric Ammonium Nitrate Dehydrogenation

  摘要：

  DOI：

  10.1021/jo961325u

文献信息

• Investigation of the asymmetric ionic Diels–Alder reaction for the synthesis of cis-decalins
  作者：James C. Anderson、Alexander J. Blake、Jonathan P. Graham、Claire Wilson

  DOI：10.1039/b305116a

  日期：——

  limited subset of cis-decalin structures. Diastereoselectivities of 73% and 82% have been found for the asymmetric ionic Diels-Alder reaction between the chiral acetal derivatives of cyclohex-2-enone (6) and 2-methylcyclohex-2-enone (18) with 2,3-dimethyl-1,3-butadiene (7). Terminal substituents on the diene partner in general render the system unreactive. However a synthetically useful cis-decalin 31

  已经开发出离子Diels-Alder反应，其中α，β-不饱和缩醛与路易斯酸或布朗斯台德酸组合形成平衡浓度的活化的亲二烯体，以提供顺式十氢化萘的对映选择性合成。（2R，3R）-丁烷-2,3-二醇的Cyclohex-2-enone型手性缩醛已针对具有各种二烯的Lewis和Brønsted酸进行了筛选，可有效合成有限的顺式十氢萘结构子集。对于环己-2-烯酮（6）和2-甲基环己-2-烯酮（18）的手性乙缩醛衍生物与2,3-二甲基-丁烯之间的不对称离子Diels-Alder反应，发现非对映选择性为73％和82％。 1,3-丁二烯（7）。二烯配偶体上的末端取代基通常使体系不反应。但是，合成上有用的顺式十氢萘31
• Highly Stereoselective Diels–Alder Reactions Catalyzed by Diboronate Complexes**
  作者：Yuan‐He Li、Su‐Lei Zhang、Yong Lu、Bo Xiao、Tian‐Yu Sun、Qian‐Qian Xu、Jia‐Hua Chen、Zhen Yang

  DOI：10.1002/anie.202303075

  日期：2023.8.14

  diboronates (BPDB) is reported. Under Lewis acid activation, they can catalyze highly exo-selective and enantioselective Diels–Alder reactions. For diactivated dienophiles, BPDB can also selectively activate one of the two carbonyl groups based on steric effect, resulting in highly regioselective asymmetric Diels–Alder reactions.

  报道了一系列易于合成、空气和水分稳定的新化合物，称为双吡咯烷二硼酸盐（BPDB）。在路易斯酸活化下，它们可以催化高度外型选择性和对映选择性狄尔斯-阿尔德反应。对于双活化亲双烯体，BPDB 还可以基于空间效应选择性地激活两个羰基之一，从而导致高度区域选择性的不对称狄尔斯-阿尔德反应。
• Stereoselective Synthesis of Dihydropyran-4-ones <i>via</i> a Formal Hetero Diels−Alder Reaction and Ceric Ammonium Nitrate Dehydrogenation
  作者：P. Andrew Evans、Jade D. Nelson

  DOI：10.1021/jo961325u

  日期：1996.1.1
• Application of Chiral Cationic Catalysts to Several Classical Syntheses of Racemic Natural Products Transforms Them into Highly Enantioselective Pathways
  作者：Qi-Ying Hu、Gang Zhou、E. J. Corey

  DOI：10.1021/ja046154m

  日期：2004.10.1

  This paper describes the application of chiral oxazaborolidinium cations of type 2 to various enantioselective Diels-Alder reactions that have served as early key steps for the syntheses of complex natural products. In the original syntheses these Diels-Alder reactions produced racemic adducts and led to racemic target molecules unless a separation of enantiomers by classical resolution was employed. By use of chiral catalysts of type 2, chiral products were obtained directly from Diels-Alder reactions of achiral components in excellent yield and enantioselectivity and with the mechanistically predicted absolute configuration. As a result, a number of classical syntheses could be converted to enantioselective versions, including (1) cortisone/cortisol (Merck/Sarett), (2) dendrobine (Kende), (3) vitamin B-12 (Eschenmoser), (4) myrocin C (Chu-Moyer/Danishefsky), (5) coriolin and hirsutene (Mehta), (6) dendrobatid 251F (Aube), (7) silphinene (Ito), and (8) nicandrenone core (Stoltz/Corey).