2,6-dimethyl-5-hydroxy-3-heptanone | 128899-84-3

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 2,6-dimethyl-5-hydroxy-3-heptanone
• 英文别名: (5S)-5-hydroxy-2,6-dimethylheptan-3-one
• CAS: 128899-84-3
• 化学式: C₉H₁₈O₂
• 分子量: 158.241
• InChiKey: RLWSGRNONJVYRO-QMMMGPOBSA-N

物化性质

• 沸点：
  232.5±13.0 °C(Predicted)
• 密度：
  0.915±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.6
• 重原子数：
  11
• 可旋转键数：
  4
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.89
• 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：

  2,6-dimethyl-5-hydroxy-3-heptanone 在 溶剂黄146 、 tetramethylammonium triacetoxyborohydride 作用下， 以 乙腈 为溶剂， 反应 2.0h， 以25.3 mg的产率得到(3S,5S)-2,6-二甲基-3,5-庚二醇
  参考文献：
  名称：

  Screening, substrate specificity and stereoselectivity of yeast strains, which reduce sterically hindered isopropyl ketones

  摘要：

  Towards the synthesis of sterically hindered optically active secondary alcohol 2, yeast strains (Candida floricola IAM 13115 and Trichosporon cutaneum IAM 12206) with si-face hydride attack on isopropyl phenylsulfonylmethyl ketone I were developed by screening. Strains with complementary re-facial selectivity (Pichia angusta IAM 12895 and Pichia minuta IAM 12215) were also found. Based on the substrate specificity studies of these four strains, microbial reduction was applied to the synthesis of (3S, 5S)-2,6-dimethyl3, 5-heptanediol 12a. (c) 2007 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetasy.2006.12.013
• 作为产物：
  描述：

  2,6-二甲基-3,5-庚二酮 在 phosphate buffer 、 葡萄糖 、 Trichosporon cutaneum IAM 12206 strain 作用下， 反应 24.0h， 生成 2,6-dimethyl-5-hydroxy-3-heptanone
  参考文献：
  名称：

  Screening, substrate specificity and stereoselectivity of yeast strains, which reduce sterically hindered isopropyl ketones

  摘要：

  Towards the synthesis of sterically hindered optically active secondary alcohol 2, yeast strains (Candida floricola IAM 13115 and Trichosporon cutaneum IAM 12206) with si-face hydride attack on isopropyl phenylsulfonylmethyl ketone I were developed by screening. Strains with complementary re-facial selectivity (Pichia angusta IAM 12895 and Pichia minuta IAM 12215) were also found. Based on the substrate specificity studies of these four strains, microbial reduction was applied to the synthesis of (3S, 5S)-2,6-dimethyl3, 5-heptanediol 12a. (c) 2007 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetasy.2006.12.013

文献信息

• An Improved Asymmetrically-Modified Nickel Catalyst Prepared from Ultrasonicated Raney Nickel
  作者：Akira Tai、Tadashi Kikukawa、Takashi Sugimura、Yoshihisa Inoue、Satoshi Abe、Tsutomu Osawa、Tadao Harada

  DOI：10.1246/bcsj.67.2473

  日期：1994.9

  The ultrasonic irradiation of Raney nickel catalyst in water followed by the removal of the resulting turbid supernatant gave an excellent nickel catalyst (RNi-U) which generated an asymmetrically-modified nickel catalyst. An EPMA (SEM-EDX) study indicated that RNi-U consisted of a fairly pure nickel surface of homogeneous size. Tartaric acid–NaBr-modified RNi-U (TA–NaBr–MRNi-U) showed a high enantio-differentiating

  对水中的 Raney 镍催化剂进行超声波辐照，然后去除混浊的上清液，得到了一种极好的镍催化剂 (RNi-U)，它生成了一种不对称改性的镍催化剂。EPMA (SEM-EDX) 研究表明 RNi-U 由均匀尺寸的相当纯的镍表面组成。酒石酸-NaBr 改性的 RNi-U（TA-NaBr-MRNi-U）在前手性酮（例如 1,3-二酮和 3-氧代链烷酸酯）的氢化中显示出高对映分化能力和反应性。
• Catalytic Meerwein-Ponndorf-Verley (MPV) and Oppenauer (OPP) Reactions: Remarkable Acceleration of the Hydride Transfer by Powerful Bidentate Aluminum Alkoxides
  作者：Keiji Maruoka、Takashi Ooi、Tomoya Miura、Yoshifumi Itagaki、Hayato Ichikawa

  DOI：10.1055/s-2002-19802

  日期：——

  the conventional MPV reduction with stoichiometric Al(i-PrO) 3 resulted in the recovery of the starting ketone under similar conditions. Our approach also enabled the reverse reaction of MPV reduction, i.e., Oppenauer (OPP) oxidation in a truly catalytic manner. Furthermore, these findings prompted us to develop a simultaneous intramolecular reduction/oxidation of hydroxy carbonyl substrates via the

  通过采用 (2,7-二甲基-1,8-联苯二氧基)双(二烷氧基铝) (3) 作为催化剂，设计了一种用于 Meerwein-Ponndorf-Verley (MPV) 还原的高效催化程序。例如，在催化量的原位生成的 3a (1 mol%) 的存在下，以 i-PrOH (1 equiv) 作为氢化物源在 CH 2 Cl 2 中还原 4-苯基环己酮在室温下在 I 内顺利进行。小时以82%的分离产率提供4-苯基环己醇。与此形成鲜明对比的是，使用化学计量 Al(i-PrO) 3 的常规 MPV 还原导致在类似条件下回收起始酮。我们的方法还能够以真正催化的方式实现 MPV 还原的逆反应，即 Oppenauer (OPP) 氧化。此外，这些发现促使我们在二齿铝催化剂 1 的存在下通过 MPV 反应过程同时开发羟基羰基底物的分子内还原/氧化，其中发生了从仲醇部分到远程羰基的高度化学选择性氢化物转移。最后，我们证明了现代
• Catalytic, high-speed tishchenko reaction using (2,7-dimethyl-1,8-biphenylenedioxy)bis(diisopropoxyaluminum) as a powerful bidentate catalyst
  作者：Takashi Ooi、Tomoya Miura、Keisuke Takaya、Keiji Maruoka

  DOI：10.1016/s0040-4039(99)01555-5

  日期：1999.10

  Exceedingly high-speed Tishchenko reaction of various aldehydes can be realized by using a powerful, bidentate aluminum catalyst. This catalytic system is also applicable to the highly stereoselective intramolecular Tishchenko reduction of β-hydroxy ketones.

  通过使用功能强大的双齿铝催化剂，可以实现各种醛类的超高速Tishchenko反应。该催化系统也适用于β-羟基酮的高度立体选择性的分子内Tishchenko还原。
• Methods
  申请人：Sattentau James Quentin

  公开号：US20070110759A1

  公开（公告）日：2007-05-17

  The presence of aldehydic groups on proteins and lipoproteins is associated with various pathological conditions such as atherosclerosis, diabetes and alcoholic liver disease. Respiratory syncytial virus (RSV) is a major cause of severe respiratory disease in infants and the elderly. RSV vaccine research has been impeded because a formalin-inactivated vaccine used in the 1960s predisposed infants to enhanced disease following subsequent natural infection. The molecular basis for the vaccine-induced hypersensitivity has not, however, been elucidated. We show here that addition of reactive carbonyl groups to ovalbumin (OVA) by treatment with glycolaldehyde or formaldehyde increases the protein's immunogenicity in mice, and biases the immune response towards a Th2-type response. The increased immunogenicity and the Th2-type response can both be abrogated by reductive elimination of the reactive carbonyl groups. We demonstrate that RSV inactivated by formaldehyde (FI-RSV), following a protocol used previously to prepare the vaccine, contains reactive carbonyl groups. Using a well-established model of FI-RSV vaccine-induced pathology, immunisation of mice with FI-RSV and subsequent challenge of the mice with live RSV induced Th2-type responses, lung eosinophilia and weight loss that were abrogated by reductive elimination of the reactive carbonyl groups. We thus propose that the addition of reactive carbonyl groups to RSV during inactivation is the major mechanism that drives the Th2-immune response and associated pathology. Moreover, we suggest that the addition of reactive carbonyl groups to other antigens, including vaccines, may be responsible for other hypersensitive and allergic reactions described in the literature.
• Screening, substrate specificity and stereoselectivity of yeast strains, which reduce sterically hindered isopropyl ketones
  作者：Chihiro Hiraoka、Masaaki Matsuda、Yuya Suzuki、Shigeo Fujieda、Mina Tomita、Ken-ichi Fuhshuku、Rika Obata、Shigeru Nishiyama、Takeshi Sugai

  DOI：10.1016/j.tetasy.2006.12.013

  日期：2006.12

  Towards the synthesis of sterically hindered optically active secondary alcohol 2, yeast strains (Candida floricola IAM 13115 and Trichosporon cutaneum IAM 12206) with si-face hydride attack on isopropyl phenylsulfonylmethyl ketone I were developed by screening. Strains with complementary re-facial selectivity (Pichia angusta IAM 12895 and Pichia minuta IAM 12215) were also found. Based on the substrate specificity studies of these four strains, microbial reduction was applied to the synthesis of (3S, 5S)-2,6-dimethyl3, 5-heptanediol 12a. (c) 2007 Elsevier Ltd. All rights reserved.