4,4-bis((tert-butyldiphenylsilyloxy)methyl)-2-methylhept-6-ynal | 1228504-78-6

• 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: 4,4-bis((tert-butyldiphenylsilyloxy)methyl)-2-methylhept-6-ynal
• 英文别名: 4,4-Bis[[tert-butyl(diphenyl)silyl]oxymethyl]-2-methylhept-6-ynal
• CAS: 1228504-78-6
• 化学式: C₄₂H₅₂O₃Si₂
• 分子量: 661.044
• InChiKey: YCDQXPBKZIHUEU-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  7.37
• 重原子数：
  47
• 可旋转键数：
  16
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.36
• 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：

  4,4-bis((tert-butyldiphenylsilyloxy)methyl)-2-methylhept-6-ynal 在 copper(II) bis(trifluoromethanesulfonate) 、 环己胺 、 三苯基膦 作用下， 以 1,2-二氯乙烷 为溶剂， 反应 22.0h， 以94%的产率得到4,4-bis[(tert-butyldiphenylsiloxy)methyl]-1-methyl-2-methylenecyclopentanecarbaldehyde
  参考文献：
  名称：

  铜(I)和伯胺协同催化的甲酰基炔烃的室温碳环化

  摘要：

  描述了一种有效的 CuI/胺催化系统，用于室温下 α-二取代甲炔的碳环化。将氨基催化与铜（I）催化的炔烃活化相结合，可以在温和条件下实现多种功能化底物的清洁碳环化。这种新型协同催化系统允许形成各种碳环和杂环，包括吡咯烷，收率良好。还讨论了该过程的机械方面。

  DOI：

  10.1002/ejoc.201100464
• 作为产物：
  描述：

  2-(4,4-bis((tert-butyldiphenylsilyloxy)methyl)hept-6-yn-2-yl)-1,3-dioxolane 在 甲酸 作用下， 以 1,4-二氧六环 、 水 为溶剂， 以92%的产率得到4,4-bis((tert-butyldiphenylsilyloxy)methyl)-2-methylhept-6-ynal
  参考文献：
  名称：

  Combined InCl₃- and Amine-Catalyzed Intramolecular Addition of α-Disubstituted Aldehydes onto Unactivated Alkynes

  摘要：

  The combination of enamine-type catalysis to the indium-catalyzed activation of alkynes allows the efficient preparation of functionalized cyclopentanes bearing a quaternary stereogenic center. A broad range of formylalkynyl derivatives has been prepared. The InCl3/(Cy)(i-Pr)NH system efficiently promotes the carbocyclization reaction of alpha-disubstituted aldehydes in good to excellent yields.

  DOI：

  10.1021/ol100729t

文献信息

• Cooperative Copper(I) and Primary Amine Catalyzed Room-Temperature Carbocyclization of Formyl Alkynes
  作者：Benjamin Montaignac、Maxime R. Vitale、Virginie Ratovelomanana-Vidal、Véronique Michelet

  DOI：10.1002/ejoc.201100464

  日期：2011.7

  An efficient CuI/amine catalytic system is described for the carbocyclization of α-disubstituted formylalkynes at room temperature. Merging aminocatalysis to the copper(I)-catalyzed activation of alkynes led to clean carbocyclization of a wide range of functionalized substrates under mild conditions. This novel cooperative catalytic system allowed the formation of a variety of carbo- and heterocycles

  描述了一种有效的 CuI/胺催化系统，用于室温下 α-二取代甲炔的碳环化。将氨基催化与铜（I）催化的炔烃活化相结合，可以在温和条件下实现多种功能化底物的清洁碳环化。这种新型协同催化系统允许形成各种碳环和杂环，包括吡咯烷，收率良好。还讨论了该过程的机械方面。
• Copper(i)–amine metallo-organocatalyzed synthesis of carbo- and heterocyclic systems
  作者：Benjamin Montaignac、Victor Östlund、Maxime R. Vitale、Virgnie Ratovelomanana-Vidal、Véronique Michelet

  DOI：10.1039/c2ob06449a

  日期：——

  and atom economical synthesis of 5-membered cyclic structures has been achieved through the combination of amino catalysis and metal catalysis. The discovery of a novel metallo-organocatalytic system merging the use of a catalytic copper(I) complex and a catalytic amount of cyclohexylamine allowed the room temperature preparation of a broad range of skeletons such as cyclopentanes, indanes, pyrrolidines

  通过氨基催化和金属催化的结合，实现了五元环状结构的高效，原子经济的合成。结合催化铜（I）配合物和催化量的铜（I）的新型金属-有机催化体系的发现。环己胺 可以在室温下制备各种骨架，例如环戊烷，茚满，吡咯烷和 四氢呋喃，是许多生物学相关分子的重要结构核心。提出了力学研究。
• InCl₃/CyNH₂ Cocatalyzed Carbocyclization Reaction: An Entry to α-Disubstituted <i>exo</i>-Methylene Cyclopentanes
  作者：Benjamin Montaignac、Maxime R. Vitale、Virginie Ratovelomanana-Vidal、Véronique Michelet

  DOI：10.1021/jo1018552

  日期：2010.12.3

  An efficient and cheap synthetic approach to functionalized exo-methylene cyclopentanes has been developed from alpha-disubstituted formyl-alkynes by merging amine catalysis with the indium activation of alkynes. We uncovered the crucial role of the amine cocatalyst and the development of a new cooperative catalytic system allowed the cyclization of a broad range of substrates. A mechanistic study was realized in order to rationalize the determining influence of the amine cocatalyst.
• Synergistic Iron-and-Amine Catalysis in Carbocyclizations
  作者：Véronique Michelet、Virginie Ratovelomanana-Vidal、Chandrasekaran Praveen、Sabine Levêque、Maxime Vitale

  DOI：10.1055/s-0033-1338612

  日期：——

  the direct intramolecular addition of aldehydes to non-activated alkynes. Accordingly, the carbocyclizations of a range of formyl-alkynes afforded the corresponding cyclopentanes in good to excellent yields. Experimental evidence tends to support a synergistic enamine/π-activation reaction mechanism. The fruitful merger of iron catalysis to amine catalysis was successfully applied in the direct intramolecular

  专用于最大Malacria教授在他的65之际个生日 抽象 铁催化与胺催化的卓有成效的合并成功地将醛类直接分子内加成到未活化的炔烃中。因此，一系列甲酰基-炔烃的碳环化以良好或优异的产率提供了相应的环戊烷。实验证据倾向于支持协同的烯胺/π-活化反应机制。 铁催化与胺催化的卓有成效的合并成功地将醛类直接分子内加成到未活化的炔烃中。因此，一系列甲酰基-炔烃的碳环化以良好或优异的产率提供了相应的环戊烷。实验证据倾向于支持协同的烯胺/π-活化反应机制。
• Combined InCl₃- and Amine-Catalyzed Intramolecular Addition of α-Disubstituted Aldehydes onto Unactivated Alkynes
  作者：Benjamin Montaignac、Maxime R. Vitale、Veronique Michelet、Virginie Ratovelomanana-Vidal

  DOI：10.1021/ol100729t

  日期：2010.6.4

  The combination of enamine-type catalysis to the indium-catalyzed activation of alkynes allows the efficient preparation of functionalized cyclopentanes bearing a quaternary stereogenic center. A broad range of formylalkynyl derivatives has been prepared. The InCl3/(Cy)(i-Pr)NH system efficiently promotes the carbocyclization reaction of alpha-disubstituted aldehydes in good to excellent yields.