4,4-bis(benzyloxymethyl)-2-methylhept-6-ynal | 1011266-03-7

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: 4,4-bis(benzyloxymethyl)-2-methylhept-6-ynal
• 英文别名: 2-Methyl-4,4-bis(phenylmethoxymethyl)hept-6-ynal；2-methyl-4,4-bis(phenylmethoxymethyl)hept-6-ynal
• CAS: 1011266-03-7
• 化学式: C₂₄H₂₈O₃
• 分子量: 364.485
• InChiKey: NGWNDSAXWAQOLZ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4
• 重原子数：
  27
• 可旋转键数：
  12
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.38
• 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(benzyloxymethyl)-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 16.0h， 以95%的产率得到4,4-bis(benzyloxymethyl)-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(benzyloxymethyl)hept-6-yn-2-yl)-1,3-dioxolane 在 盐酸 作用下， 以 水 、 丙酮 为溶剂， 以88%的产率得到4,4-bis(benzyloxymethyl)-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

• Enantioselective metallo-organocatalyzed preparation of cyclopentanes bearing an all-carbon quaternary stereocenter
  作者：Benjamin Montaignac、Chandrasekaran Praveen、Maxime R. Vitale、Véronique Michelet、Virginie Ratovelomanana-Vidal

  DOI：10.1039/c2cc32823b

  日期：——

  Enantioselective metallo-organocatalyzed carbocyclizations of formyl-alkynes have been developed. The cooperation between aminocatalysis and a chiral copper(I) complex granted access to enantio-enriched cyclopentanes through the challenging formation of all-carbon quaternary stereocenters.

  已开发出对映选择性的金属有机催化的甲炔基碳环化反应。氨基催化与手性铜（I）配合物之间的合作通过具有挑战性的全碳四元立体中心的形成而获得了对映体富集的环戊烷。
• Enantioselective Merger of Aminocatalysis with π-Lewis Acid Metal Catalysis: Asymmetric Preparation of Carbo- and Heterocycles
  作者：Chandrasekaran Praveen、Benjamin Montaignac、Maxime R. Vitale、Virginie Ratovelomanana-Vidal、Véronique Michelet

  DOI：10.1002/cctc.201300313

  日期：2013.8

  ratio. After a careful examination of several other strategies, the best synergic catalytic system, which combines a chiral copper(I) complex with cyclohexylamine, afforded the enantioselective preparations of cyclopentane, indane, and pyrrolidine scaffolds with moderate to excellent control of the all‐carbon quaternary stereogenic centers created through such cyclization processes.

  通过氨基催化与α-二取代甲酰基炔烃的催化铟（III）或铜（I）活化的合并，描述了各种五元碳环和杂环结构的金属有机催化对映选择性合成。与（R）-1,1'-双-（2-萘胺）配体结合使用三氯化铟可产生令人鼓舞的结果，对映体比例高达85:15。在仔细研究了其他几种策略后，将手性铜（I）配合物与环己胺结合在一起的最佳协同催化系统，提供了对环戊烷，茚满和吡咯烷骨架的对映选择性制备，对中碳四元化合物的控制程度中等至优异通过这种环化过程建立的立体成因中心。
• 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.
• Direct Carbocyclization of Aldehydes with Alkynes:  Combining Gold Catalysis with Aminocatalysis
  作者：Jörg T. Binder、Benedikt Crone、Timm T. Haug、Helge Menz、Stefan F. Kirsch

  DOI：10.1021/ol800092p

  日期：2008.3.1

  A combination of gold(l) complexes and amine bases catalyzes the 5-exo-dig cyclization of formyl alkynes. This direct alpha-functionalization of aldehydes with unactivated alkynes does not involve the use of preformed enol equivalents.