(1R,5S)-6,6-dimethylbicyclo<3.1.1>heptan-2-ylideneacetaldehyde | 6712-92-1

• 分子结构分类: 有机化合物
• 英文名称: (1R,5S)-6,6-dimethylbicyclo<3.1.1>heptan-2-ylideneacetaldehyde
• 英文别名: E/Z-2(6,6-dimethylbicyclo<3.1.1>-2-heptylidene)ethanal；((1R,2Ξ)-6,6-dimethyl-norpinan-2-yliden)-acetaldehyde；((1R,2Ξ)-6,6-Dimethyl-norpinan-2-yliden)-acetaldehyd；2-[(1R,5S)-6,6-dimethyl-2-bicyclo[3.1.1]heptanylidene]acetaldehyde
• CAS: 6712-92-1；64802-75-1；64802-76-2
• 化学式: C₁₁H₁₆O
• 分子量: 164.247
• InChiKey: ZHOVMZLXBCUUFS-UWVGGRQHSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.57
• 重原子数：
  12.0
• 可旋转键数：
  1.0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.73
• 拓扑面积：
  17.07
• 氢给体数：
  0.0
• 氢受体数：
  1.0

反应信息

• 作为反应物：
  描述：

  (1R,5S)-6,6-dimethylbicyclo<3.1.1>heptan-2-ylideneacetaldehyde 在 sodium hydroxide 、 草酰氯 、 silver nitrate 、 zinc(II) chloride 作用下， 以 乙醚 、 乙醇 、 水 、 苯 为溶剂， 反应 27.0h， 生成 (2R,2'R,4'S)-5,7-dihydroxy-3',3'-dimethyl-2',4'-methanospiro-4-one
  参考文献：
  名称：

  The Synthesis of (-)-Robustadial A and Some Analogues.

  摘要：

  The naturally occurring chroman derivative, robustadial A, and several analogues have been prepared by a four-step synthesis starting from phloroglucinol. The synthetic scheme involves as the first step a Friedel-Crafts condensation of an alpha,beta-unsaturated acid derivative with phloroglucinol to the corresponding chromanone. The isobutyl group at the 4-position was introduced with methallylzine bromide followed by hydrogenation, carried out as a one-pot reaction. Finally, both aldehyde functions were attached using dichloromethyl methyl ether and titanium tetrachloride. Optically pure 6,6-dimethylbicyclo[3.1.1]heptan-2-ylidene-acetic acid, needed for the synthesis of robustadial, was prepared from (-)-nopol by two consecutive oxidations in 77% overall yield.

  DOI：

  10.3891/acta.chem.scand.50-0132
• 作为产物：
  描述：

  (1R)6,6-二甲基联环(3.1.1)庚烷-2-烯-2-乙醇 在 (COCl₂)2 、 二甲基亚砜 、 三乙胺 作用下， 生成 (1R,5S)-6,6-dimethylbicyclo<3.1.1>heptan-2-ylideneacetaldehyde
  参考文献：
  名称：

  The Synthesis of (-)-Robustadial A and Some Analogues.

  摘要：

  The naturally occurring chroman derivative, robustadial A, and several analogues have been prepared by a four-step synthesis starting from phloroglucinol. The synthetic scheme involves as the first step a Friedel-Crafts condensation of an alpha,beta-unsaturated acid derivative with phloroglucinol to the corresponding chromanone. The isobutyl group at the 4-position was introduced with methallylzine bromide followed by hydrogenation, carried out as a one-pot reaction. Finally, both aldehyde functions were attached using dichloromethyl methyl ether and titanium tetrachloride. Optically pure 6,6-dimethylbicyclo[3.1.1]heptan-2-ylidene-acetic acid, needed for the synthesis of robustadial, was prepared from (-)-nopol by two consecutive oxidations in 77% overall yield.

  DOI：

  10.3891/acta.chem.scand.50-0132

文献信息

• Metal-free one-pot α-carboxylation of primary alcohols
  作者：Gydo van der Heijden、Jasper Kraakman、Jasper Biemolt、Eelco Ruijter、Romano V. A. Orru

  DOI：10.1039/c6ob01813k

  日期：——

  An efficient metal-free procedure for the formal α-carboxylation of primary alcohols has been developed. The method involves a one-pot oxidation/Passerini/hydrolysis sequence and provides access to α-hydroxy acids bearing a broad range of functional groups. A minor modification to the reaction conditions extends the range of accessible products to α-hydroxy esters.

  已经开发出一种有效的无金属的伯醇形式α-羧化方法。该方法涉及一锅氧化/ Passerini /水解顺序，并提供了带有多种官能团的α-羟基酸的通道。对反应条件的微小改动将可及产品的范围扩展至α-羟基酯。
• Synthese de pyridines par cyclisation de systemes azatrieniques
  作者：G. Dauphin、B. Jamilloux、A. Kergomard、D. Planat

  DOI：10.1016/0040-4020(77)80403-1

  日期：——

  The cyclisation of imines from α,β-unsaturated aldehydes and allylamine to pyridines has been studied. At 25°, the catalytic action of the basic system sodium-alloocimene gives a first type of cyclisation binding the α carbon of the amino chain to the δ carbon of the aldehydic one. Arguments in favour of a carbanionic cyclisation are advanced. A second type of cyclisation is observed in the case of

  已经研究了亚胺从α，β-不饱和醛和烯丙胺到吡啶的环化作用。在25°时，碱性系统钠-烯丙基铝的催化作用产生了第一种环化反应，该环化反应将氨基链的α碳与醛基的δ碳结合。提出了支持碳负离子环化的论点。在3-氮杂六烯烯体系的情况下观察到第二种环化，该体系在没有任何催化体系的情况下在120°产生吡啶。在文献中没有描述这种类型的反应，并且看起来纯粹是热的。
• One-pot synthesis of precocene I and II and a formal synthesis of robustadial A and B via 2-phenyl-4<i>H</i>-1,3,2-benzodioxaborin
  作者：Suzanne Bissada、Cheuk K. Lau、Michael A. Bernstein、Claude Dufresne

  DOI：10.1139/v94-237

  日期：1994.8.1

  The reaction of a phenol, and α,β-unsaturated aldehyde, and phenylboronic acid yields a 2-phenyl-4H-1,3,2-benzodioxaborin. Upon heating, this compound decomposes to an orthoquinone-methide intermediate, which undergoes an electrocyclization reaction to a chromene ring system. This method has been applied to the synthesis of precocenes I and II and the robustadial A and B.

  苯酚、α,β-不饱和醛和苯硼酸的反应产生2-苯基-4H-1,3,2-苯并二氧硼杂环。加热后，该化合物分解为一个邻醌甲烯中间体，该中间体经历电环化反应形成一个咔啉环系统。这种方法已应用于合成早生素I和II以及强健二烯醇A和B。
• Zur Kenntnis homologer Alkohole der Terpen- und Sesquiterpenreihe. III. Mitteilung: Oxydation β, γ-ungesättigter Alkohole
  作者：Günther Ohloff

  DOI：10.1002/ardp.19542870504

  日期：——
• Ohloff, Justus Liebigs Annalen der Chemie, 1959, vol. 627, p. 79,91
  作者：Ohloff

  DOI：——

  日期：——