2,2-dimethylhex-5-en-1-al | 52278-99-6

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 2,2-dimethylhex-5-en-1-al
• 英文别名: 2,2-dimethylhex-5-enal；2,2-dimethyl-5-hexenal
• CAS: 52278-99-6
• 化学式: C₈H₁₄O
• 分子量: 126.199
• InChiKey: KGRGYLRBOKDMAX-UHFFFAOYSA-N

物化性质

• 沸点：
  156.7±19.0 °C(Predicted)
• 密度：
  0.824±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.1
• 重原子数：
  9
• 可旋转键数：
  4
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.62
• 拓扑面积：
  17.1
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  2,2-dimethylhex-5-en-1-al 在 lithium aluminium tetrahydride 、 碘 、 一水合肼 、 三乙胺 作用下， 以 四氢呋喃 、 乙醚 、 乙醇 为溶剂， 反应 22.0h， 生成 1,1,3-三甲基环戊烷
  参考文献：
  名称：

  Mechanism of Reaction of Geminal Dihalides with Lithium Aluminum Hydride. Evidence for Single Electron Transfer as the Major Reaction Pathway

  摘要：

  The reactions of a sterically hindered geminal dichloride 4a and the corresponding diiodide 4b with LiAlH4 (LAH) were found to involve an electron-transfer mechanism. Whereas the monochloro analog of 4a (8) is inert toward LAH, 4a was more reactive. Observation of radical-derived products in the reaction of 4a with LAH indicates that the presence of two chlorine atoms on the same carbon atom results in a favorable reduction potential for 4a, as compared to 8. These results show that LAH can function as a one-electron donor toward geminal dichlorides. It was found that the diiodo analog 4b is more reactive toward LAH than 4a due to the inherent favorable reduction potentials of alkyl iodides compared to chlorides. The reactivity of 4b toward LAH was also found to be greater than that of the monoiodo analog (Ib) in keeping with the more favorable reduction potential of the diiodide (4b) compared to the monoiodide (Ib). The rates of cyclization of the corresponding haloalkyl radicals generated from 4a and 4b were also determined and were found to be 7.4 x 10(5)/s for the chloroalkyl and 5.5 x 10(5)/s for the iodoalkyl radical at 25 degrees C. The formation of small amounts of the carbene-derived product, 5, in the reactions of both 4a and 4b with LAH appeared to be preceded by a radical intermediate.

  DOI：

  10.1021/jo00093a011
• 作为产物：
  描述：

  2,2-二甲基-5-己烯-1-醇 在 pyridinium chlorochromate 作用下， 以 二氯甲烷 为溶剂， 生成 2,2-dimethylhex-5-en-1-al
  参考文献：
  名称：

  调节烷氧基自由基从环化到 1,2-甲硅烷基转移的反应性：β-取代环醇的立体选择性合成

  摘要：

  在此，我们报告了一种非对映选择性构建β-取代的环戊醇和环丁醇的激进策略。反应的成功归因于在烷氧基环化为烯烃时有利的自由基 1,2-甲硅烷基转移。该反应显示出广泛的底物范围和广泛的官能团耐受性。该方法的合成潜力在克级反应和各种螺环化合物的简便合成中得到了证明。

  DOI：

  10.1021/acs.orglett.2c00428

文献信息

• Silver-Catalyzed, Manganese-Mediated Allylation and Benzylation Reactions of Aldehydes and Ketones
  作者：Nicholas T. Barczak、Elizabeth R. Jarvo

  DOI：10.1002/ejoc.200800898

  日期：2008.11

  aldehydes and ketones using unactivated manganese powder. Aliphatic and aromatic aldehydes and ketones react, and aryl chlorides, nitriles, electron-donating and electron-withdrawing groups are tolerated. Benzylation using benzyl bromide also proceeds smoothly under these reaction conditions. Preliminary mechanistic studies are consistent with the formation a nucleophilic allylmetal intermediate. (©

  溴化银使用未活化的锰粉催化醛和酮的 Barbier 型烯丙基化。脂肪族和芳香族醛和酮反应，并且允许芳基氯、腈、给电子和吸电子基团。在这些反应条件下，使用苄基溴的苄基化也能顺利进行。初步机理研究与亲核烯丙基金属中间体的形成一致。(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008)
• Concerning the preparation of geminal digrignard reagents.
  作者：Fabio Doctorovich、Abhay K. Deshpande、E.C. Ashby

  DOI：10.1016/s0040-4020(01)90449-1

  日期：1994.1

  Mechanistic studies of the reactions of geminal dihalides with magnesium and sodium have been carried out and the possibility of preparing geminal DiGrignard Reagents for use in situ has been explored.

  已经进行了双金属卤化物与镁和钠反应的机理研究，并探索了制备双基吉尼亚试剂原位使用的可能性。
• Stereoselective Formation of Fused Tricyclic Amines from Acyclic Aldehydes by a Cascade Process Involving Condensation, Cyclization, and Dipolar Cycloaddition
  作者：Adam J. M. Burrell、Iain Coldham、Luke Watson、Niall Oram、Christopher D. Pilgram、Nathaniel G. Martin

  DOI：10.1021/jo8019913

  日期：2009.3.20

  halide or dipolarophile has been studied. Several primary amines including simple amino acids such as glycine, alanine, and phenylalanine and derivatives such as glycine ethyl ester and also hydroxylamine have been investigated. High yields are obtained in the formation of different tricyclic ring sizes; the dipolar cycloaddition necessarily creates a five-membered ring, and we have investigated the formation

  由无环前体制备三环胺的方法是使用一系列串联反应，包括醛与伯胺的缩合，环化（取代卤化物），然后原位去质子化或脱羧以得到甲亚胺叶立德或硝酮。通过分子内偶极环加成。该方法简单明了，使用腈烷基化反应再进行DIBAL-H还原，可轻松，快速，高产率地制备醛类前体。已经研究了醛和卤化物或亲双氟体之间具有不同系链长度的各种底物的相对易反应性。已经研究了几种伯胺，包括简单氨基酸，例如甘氨酸，丙氨酸和苯丙氨酸，以及衍生物例如甘氨酸乙酯和羟胺。通过形成不同的三环尺寸可获得高收率；偶极环加成必然会形成一个五元环，而我们已经研究了另外两个新环尺寸的五元环和六元环的形成。在所有情况下，收率都很高（除非当使用甘氨酸时，与末端链烯烃亲和性的系链导致六元环），最有效的方法是形成其中形成所有五元环的三环产物。用炔烃作为双亲性物的例子也是成功的。在所有研究的反应中，形成的产物具有完全的区域选择性，并且显着地具有完全的立体选择性
• Enantio‐ and Diastereoselective, Lewis Base Catalyzed, Cascade Sulfenoacetalization of Alkenyl Aldehydes
  作者：Anastassia Matviitsuk、Scott E. Denmark

  DOI：10.1002/anie.201906535

  日期：2019.9.2

  catalytic, enantio-, and diastereoselective formation of sulfenyl acetals bearing multiple stereogenic centers is reported. Alkenyl aldehydes undergo a chiral thiiranium ion initiated cascade starting with intramolecular capture by a formyl group and termination by capture with HFIP solvent. This method provides a one-pot synthesis of dihydropyran and 1,3-disubstituted isochroman acetals in good to excellent

  据报道，带有多个立体中心的亚硫基乙缩醛催化，对映体和非对映体选择性形成。烯基醛经历手性噻吩鎓离子引发的级联反应，首先通过甲酰基进行分子内捕获，然后通过用HFIP溶剂捕获而终止。该方法可以一锅法合成二氢吡喃和1,3-二取代的异苯并二氢吡喃缩醛，收率好至极好，非对映异构体含量高（高达> 99：1 dr），对映体控制（高达99：1 er）。
• The Scope and Limitations of 1,3-Stannyl Shift-Promoted Intramolecular Cyclizations of α-Stannyl Radicals with a Formyl Group
  作者：Shau-Hua Ueng、Ming-Jen Chen、Shu-Fang Chu、Yar-Fang Shao、Gang-Ting Fan、Sheng-Yueh Chang、Yeun-Min Tsai

  DOI：10.1021/jo052176v

  日期：2006.2.1

  and serves as a driving force to promote the cyclizations. Although the cyclization rates can be accelerated when the formyl group carries α-dimethyl substituents, unfortunately β-scission of the alkoxy radicals becomes competitive with the 1,3-stannyl shift. The β-stannyloxy radicals can be employed in further cyclizations to obtain tandem cyclization products.

  α-三丁基锡烷基可以由相应的溴化物或黄药生成。这些基团经过带有甲酰基的有效分子内1，5-环化反应。所得的β-锡烷基烷氧基通过从碳到氧的1，3-锡烷基转移进行，以提供β-锡烷基氧基。这种新颖的重排极有可能是不可逆的，并且是促进环化的驱动力。尽管当甲酰基带有α-二甲基取代基时可以加快环化速率，但是不幸的是，烷氧基的β-断裂与1，3-锡烷基移位竞争。可以将β-锡烷基氧基用于进一步的环化以获得串联环化产物。