4-hydroxy-5-methyl-3-methylene-hexan-2-one | 73255-32-0

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 4-hydroxy-5-methyl-3-methylene-hexan-2-one
• 英文别名: 4-Hydroxy-5-methyl-3-methylidenehexan-2-one
• CAS: 73255-32-0
• 化学式: C₈H₁₄O₂
• 分子量: 142.198
• InChiKey: NVWLYPGCOZGDDY-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1
• 重原子数：
  10
• 可旋转键数：
  3
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.62
• 拓扑面积：
  37.3
• 氢给体数：
  1
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  4-hydroxy-5-methyl-3-methylene-hexan-2-one 在 titanium(IV) isopropylate 、 叔丁基过氧化氢 、 4 A molecular sieve 作用下， 以 异辛烷 、 二氯甲烷 为溶剂， 以70%的产率得到syn-3-methylene epoxy-4-hydroxy-5-methyl-hexan-2-one
  参考文献：
  名称：

  Asymmetric metal-catalysed epoxidation of electron-deficient olefins

  摘要：

  The SYN diastereospecific epoxidation of acyclic beta-hydroxyketones (beta-hydroxyacrylates) and cyclic beta-hydroxyketones using titanium and vanadium catalysts is reported. Some initial results on the asymmetric epoxidation of these systems using the Sharpless titanium-tartrate catalyst are also described.

  DOI：

  10.1016/s0957-4166(00)86103-0
• 作为产物：
  描述：

  异丁醛 、 3-丁炔-2-酮 在 N-甲基吲哚酮 、 二异丁基氢化铝 作用下， 以 四氢呋喃 、 正己烷 为溶剂， 反应 4.0h， 以80%的产率得到4-hydroxy-5-methyl-3-methylene-hexan-2-one
  参考文献：
  名称：

  Ramachandran, P. Veeraraghavan; Reddy, M. Venkat Ram; Rudd, Michael T., Chemical Communications, 1999, # 19, p. 1979 - 1980

  摘要：

  DOI：

文献信息

• Rhodium-Catalyzed Formation of Stereocontrolled Trisubstituted Alkenes from Baylis-Hillman Adducts
  作者：Thomas Gendrineau、Nicolas Demoulin、Laure Navarre、Jean-Pierre Genet、Sylvain Darses

  DOI：10.1002/chem.200802276

  日期：2009.4.27

  Efficient and general conditions for the formation of stereodefined trisubstituted alkenes by using the rhodium‐catalyzed reaction of unactivated Baylis–Hillman adducts with either organoboronic acids or potassium trifluoro(organo)borates are reported (see scheme).

  据报道，通过铑催化未活化的Baylis-Hillman加合物与有机硼酸或三氟（有机）硼酸钾的反应，可形成立体定义的三取代烯烃的高效通用条件（参见方案）。
• Rhodium(I)- or ruthenium(II)-catalyzed direct coupling of vinyl ketones with aldehydes and the subsequent reduction to give aldol derivatives anti-selectively
  作者：Susumu Sato、Isamu Matsuda、Masahiro Shibata

  DOI：10.1016/0022-328x(89)80096-8

  日期：1989.11

  A vinyl ketone reacts with an aldehyde to give an α-methylene-β-hydroxyalkanone with the concomitant formation of the vinyl ketone dimer in the presence of catalytic amount of RhH(PPh3)4 or RuH2(PPh3)4 under almost neutral conditions. The selectivity of the cross-coupling product is remarkably improved in the presence of an extra mole of aldehyde. This type of cross-coupling is explained by the intermediacy

  在催化量的RhH(PPh 3 ) 4或RuH 2 (PPh 3 ) 4存在下，在几乎中性的条件下，乙烯基酮与醛反应生成α-亚甲基-β-羟基烷酮，同时形成乙烯基酮二聚体状况。在额外摩尔醛的存在下，交叉偶联产物的选择性显着提高。这种类型的交叉偶联可以通过过渡金属烯醇化物的中间作用来解释，过渡金属烯醇化物是通过 MH 与乙烯基酮的迈克尔型加成形成的。随后在催化剂存在下，α-亚甲基-β-羟基烷酮的碳-碳双键容易发生氢化反应，得到羟醛衍生物。 [Rh(COD)(DPPB)]PF 6 ，[COD = 1,5-环辛二烯，DPPB = 1,4-双(二苯基膦)丁烷]是催化剂的最佳选择，并反选择性地产生羟醛衍生物。因此，所描述的两步操作在几乎中性条件下通过反选择性途径提供羟醛衍生物。
• A FACILE COUPLING REACTION OF VINYL KETONES WITH ALDEHYDES CATALYZED BY RHODIUM(I) HYDRIDE COMPLEX
  作者：Susumu Sato、Isamu Matsuda、Yusuke Izumi

  DOI：10.1246/cl.1985.1875

  日期：1985.12.5

  A convenient α-hydroxyalkylation of vinyl ketones is accomplished by the coupling reaction of vinyl ketone and aldehyde, where rhodium(I) enolate derived from HRh(PPh3)4 plays an important role in the carbon–carbon bond forming step.

  乙烯基酮的方便的 α-羟烷基化是通过乙烯基酮和醛的偶联反应完成的，其中衍生自 HRh(PPh3)4 的铑（I）烯醇化物在碳-碳键形成步骤中起重要作用。
• Magnesium Bromide Mediated Highly Diastereoselective Heterogeneous Hydrogenation of Olefins
  作者：Abderrahim Bouzide

  DOI：10.1021/ol020032m

  日期：2002.4.1

  Palladium on carbon combined with magnesium bromide catalyzed hydrogenation of Baylis-Hillman olefins to afford the corresponding aldol derivatives in a highly syn-diastereoselective manner is described. [reaction: see text]

  描述了碳上的钯与溴化镁结合以高同-非对映选择性的方式催化Baylis-Hillman烯烃的氢化以提供相应的羟醛衍生物。[反应：看文字]
• 2,6-Diphenyl-4H-chalcogenopyran-4-ones and 2,6-diphenyl-4H-chalcogenopyran-4-thiones: a new catalyst for the Baylis-Hillman reaction
  作者：Tetsuo Iwama、Hironori Kinoshita、Tadashi Kataoka

  DOI：10.1016/s0040-4039(99)00585-7

  日期：1999.5

  2,6-Diphenyl-4H-chalcogenopyran-4-ones and 2,6-diphenyl-4H-chalcogenopyran-4-thione a new series of catalysts for the Baylis-Hillman reaction, were investigated. The reactions proceeded smoothly in the presence of 1 mol eq. of TiCl4 under atmospheric pressure at 0 degrees C, giving adducts in moderate to high yields. Chalcogenopyranones and chalcogenopyranthiones were a more efficient kind of catalyst than Me2S. (C) 1999 Elsevier Science Ltd. All rights reserved.