4-甲基-1-苯基己-5-烯-3-醇 | 83173-74-4

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 中文名称: 4-甲基-1-苯基己-5-烯-3-醇
• 英文名称: (anti)-4-hydroxy-3-methyl-6-phenyl-1-hexene
• 英文别名: anti-4-Hydroxy-3-methyl-6-phenyl-1-hexene；(u)-4-Methyl-1-phenyl-5-hexen-3-ol；4-methyl-1-phenyl-hex-5-ene-3-ol；4-methyl-1-phenylhex-5-en-3-ol；(3S,4R)-4-methyl-1-phenylhex-5-en-3-ol
• CAS: 83173-74-4；89103-73-1；89103-74-2；104011-57-6；106756-95-0；129170-74-7
• 化学式: C₁₃H₁₈O
• 分子量: 190.285
• InChiKey: PXGZVEMZSFQBCV-YPMHNXCESA-N

物化性质

• 沸点：
  307.1±21.0 °C(Predicted)
• 密度：
  0.960±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.4
• 重原子数：
  14
• 可旋转键数：
  5
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.38
• 拓扑面积：
  20.2
• 氢给体数：
  1
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  4-甲基-1-苯基己-5-烯-3-醇 在 2,6-二甲基吡啶 、 二氯苯酚溴酯 、 potassium carbonate 、 臭氧 作用下， 以 二氯甲烷 为溶剂， 反应 3.0h， 生成
  参考文献：
  名称：

  Enantioselective syn and anti Homocrotylation of Aldehydes: Application to the Formal Synthesis of Spongidepsin

  摘要：

  Whereas crotylboration has been a useful method for synthesis of stereochemically complex products, we have shown that homocrotylboration can be achieved with cyclopropanated crotylation reagents, and that the stereo-selectivity of the reaction can be predicted by analogous models. This paper presents a full account of this work, including the first examples of asymmetric anti homocrotylation. The scope of this reaction is demonstrated with highly enantioselective homocrotylation of both aliphatic and aromatic aldehydes, as well as double diastereoselection studies. An application of the synthesis of the marine natural product spongidepsin is presented, as well as streamlined syntheses of homocrotylation reagents.

  DOI：

  10.1021/jacs.5b08858
• 作为产物：
  描述：

  (3S,4R,E)-4-methyl-1-phenyl-6-(tributylstannyl)hex-5-en-3-ol 在 正丁基锂 、 氯化铵 作用下， 生成 4-甲基-1-苯基己-5-烯-3-醇
  参考文献：
  名称：

  Enantioconvergent Hydroboration of a Racemic Allene: Enantioselective Synthesis of (E)-δ-Stannyl-anti-homoallylic Alcohols via Aldehyde Crotylboration

  摘要：

  The enantioconvergent hydroboration of racemic allenylstannane (+/-)-1 with ((d)Ipc)(2)BH converts both enantiomers of (+/-)-1 into the enantioenriched crotylborane (S)-E-3. Subsequent crotylboration of aldehydes with (S)-E-3 provides (E)-stannyl-homoallylic alcohols 5 in good yields and with excellent enantioselectivity.

  DOI：

  10.1021/ja2010187

文献信息

• Silver Oxide as a Novel Catalyst for Carbon–Carbon Bond-forming Reactions in Aqueous Media
  作者：Masaharu Ueno、Arata Tanoue、Shu Kobayashi

  DOI：10.1246/cl.2010.652

  日期：2010.6.5

  Silver oxide was found to be an excellent catalyst for allylation reactions of allyltributyltins with aldehydes in aqueous media. Despite the very low solubility of silver oxide in the media, the reactions proceeded smoothly, and the catalyst was recovered and reused. When α-methyl-substituted allyltributyltin was used as the nucleophile, the corresponding α-adducts were obtained exclusively in high yields with good anti-selectivity. A reaction mechanism including transmetalation from tin to silver is proposed.

  银氧化物在烯丙基三丁锡与醛在水相中的烯丙基化反应中表现出优异的催化性能。尽管银氧化物在介质中的溶解度极低，反应仍顺利进行，且催化剂可回收并重复使用。当使用α-甲基取代的烯丙基三丁锡作为亲核试剂时，以高产率且具有良好反式选择性地获得了相应的α-加成产物。提出了一种包含从锡到银的转金属化步骤的反应机理。
• Catalytic Organic Reactions on the Surface of Silver(I) Oxide in Water
  作者：Masaharu Ueno、Arata Tanoue、Shū Kobayashi

  DOI：10.1246/cl.140818

  日期：2014.12.5

  We have developed Ag2O-catalyzed allylation reactions of aldehydes with allylsilanes in water, providing homoallylic alcohols in high yields with high anti-selectivities. It was found that the reac...

  我们开发了 Ag2O 催化的醛与烯丙基硅烷在水中的烯丙基化反应，以高产率和高抗选择性提供高烯丙醇。结果发现反应...
• Transition-Metal-Free Reductive Coupling of 1,3-Butadienes with Aldehydes Catalyzed by Dibutyliodotin Hydride
  作者：Itaru Suzuki、Yuki Uji、Shujiro Kanaya、Ryosuke Ieki、Shinji Tsunoi、Ikuya Shibata

  DOI：10.1021/acs.orglett.7b02671

  日期：2017.10.6

  In this study, the Bu2SnIH-catalyzed direct coupling of 1,3-dienes with aldehydes was developed. This reaction could be suitable for coupling without the use of transition-metal catalysts. Many types of aldehydes were applied to this reaction. The addition of MeOH promoted the catalytic cycle.

  在这项研究中，开发了Bu 2 SnIH催化的1,3-二烯与醛的直接偶联。该反应可以适合于不使用过渡金属催化剂的偶联。许多类型的醛被用于该反应。MeOH的加入促进了催化循环。
• A Novel Preparation of Allylic Trichlorotins from α,α-Diisopropylhomoallylic Alcohols and Its Application to Carbonyl Allylations
  作者：Yoshiro Masuyama、Keisuke Saeki、Sachiko Horiguchi、Yasuhiko Kurusu

  DOI：10.1055/s-2001-18102

  日期：——

  α,α-Diisopropylhomoallylic alcohols react with tin(II) chloride and NCS in CH2Cl2 at -40 °C to -60 °C to produce allylic tins and diisopropyl ketone, and the allylic tins in situ cause nucleophilic addition to aldehydes to afford α-substituted homoallylic alcohols.

  α,α-二异丙基同烯醇在-40 °C到-60 °C的条件下与氯化亚锡和NCS在CH2Cl2中反应，生成烯丙基锡和二异丙基酮，而生成的烯丙基锡在原位导致对醛的亲核加成，获得α-取代的同烯醇。
• Asymmetric allylation with chiral formamide catalysts
  作者：Katsuhiko Iseki、Shin Mizuno、Yoshichika Kuroki、Yoshiro Kobayashi

  DOI：10.1016/s0040-4020(98)01097-7

  日期：1999.1

  The successful example of chiral formamides that function as asymmetric catalysts is described. (S,S)-N,N-Bis(α-methylbenzyl)formamide mediates the enantioselective addition of allyl- and crotyltrichlorosilanes to aliphatic aldehydes with the assistance of hexamethylphosphoramide (HMPA) to afford the corresponding homoallylic alcohols in up to 98% enantiomeric excess.

  描述了用作不对称催化剂的手性甲酰胺的成功实例。（S，S）-N，N-双（α-甲基苄基）甲酰胺在六甲基磷酰胺（HMPA）的协助下，将烯丙基三甲基和巴豆基三氯硅烷对映选择性加成到脂肪族醛中，从而提供相应的均烯丙基醇，对映体过量高达98％ 。