3-hydroxy-3-propylpentane-2,4-dione | 1258306-79-4

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 3-hydroxy-3-propylpentane-2,4-dione
• 英文别名: 3-acetyl-3-hydroxy-2-hexanone；Diacetyl Butanol
• CAS: 1258306-79-4
• 化学式: C₈H₁₄O₃
• 分子量: 158.197
• InChiKey: DGTOXDJQZREZQH-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.3
• 重原子数：
  11
• 可旋转键数：
  4
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.75
• 拓扑面积：
  54.4
• 氢给体数：
  1
• 氢受体数：
  3

反应信息

• 作为产物：
  描述：

  2,3-己二酮 在 盐酸硫胺 、 三乙胺 作用下， 以 PEG₄₀₀ 为溶剂， 以65%的产率得到(RS)-3-hydroxy-3-methylheptane-2,4-dione
  参考文献：
  名称：

  α-Diketones as acyl anion equivalents: a non-enzymatic thiamine-promoted route to aldehyde–ketone coupling in PEG400 as recyclable medium

  摘要：

  By mimicking the peculiar behavior of thiamine diphosphate-dependent acetylacetoin synthase, it has been demonstrated that thiamine hydrochloride 2a and its simple analogue thiazolium salt 2b are able to activate alpha-diketones as acyl anion equivalents in nucleophilic acylations, such as the homo-coupling of alpha-diketones and the hitherto unreported cross-coupling between a-diketones and alpha-ketoesters. These carboligation reactions were optimized under stoichiometric (2a) and catalytic conditions (2b) by using eco-friendly PEG400 as the reaction medium, thus allowing both solvent and thiazolium salt recycling. (C) 2011 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tet.2011.08.056

文献信息

• Enzymatic Chemoselective Aldehyde-Ketone Cross-Couplings through the Polarity Reversal of Methylacetoin
  作者：Giovanni Bernacchia、Olga Bortolini、Morena De Bastiani、Lindomar Alberto Lerin、Sabrina Loschonsky、Alessandro Massi、Michael Müller、Pier Paolo Giovannini

  DOI：10.1002/anie.201502102

  日期：2015.6.8

  α‐hydroxy ketones through the rare aldehyde–ketone cross‐carboligation reaction. Unprecedented is the use of methylacetoin as the acetyl anion donor in combination with a range of strongly to weakly activated ketones. In some cases, Ao:DCPIP OR produced the desired tertiary alcohols with stereochemistry opposite to that obtained with other ThDP‐dependent enzymes. The combination of methylacetoin as acyl anion

  克隆了地衣芽孢杆菌的乙硫胺二磷酸（ThDP）依赖性酶乙酰化酶：二氯苯酚吲哚酚氧化还原酶（Ao：DCPIP OR），并在大肠杆菌中过表达。该重组酶与从地衣芽孢杆菌中部分纯化的乙酰乙酰辅酶合酶（AAS）具有相似的相似性，表明它们可能是同一酶。通过罕见的醛-酮交叉羰基化反应，重组Ao：DCPIP OR的产品范围扩展到手性叔α-羟基酮。前所未有的是，将甲基乙酰缩丁酮作为乙酰基阴离子供体与一系列强活化至弱活化的酮结合使用。在某些情况下，Ao：DCPIP OR产生所需的叔醇，其立体化学与其他ThDP依赖酶获得的立体化学相反。a不对称合成中的C键形成。
• Expanding the scope of enzymatic carboligation reactions in flow-mode: production of optically active tertiary alcohols with packed-bed micro-bioreactors
  作者：P. P. Giovannini、O. Bortolini、A. Cavazzini、R. Greco、G. Fantin、A. Massi

  DOI：10.1039/c4gc00838c

  日期：——

  Acetylacetoin synthase (AAS) from Bacillus licheniformis has been partially purified and immobilized on a silica support and its activity was tested under batch conditions in the homo-coupling of a set of α-diketones leading to valuable α-hydroxy ketone derivatives displaying a chiral tertiary alcohol functionality at the α-position. Next, the effectiveness of AAS heterogeneous catalysis has been evaluated

  地衣芽孢杆菌的乙酰丙酮化合酶（AAS）该化合物已部分纯化并固定在二氧化硅载体上，并在一批α-二酮的均相偶联中分批条件下测试了其活性，从而生成了宝贵的α-羟基酮衍生物，在α位上显示了手性叔醇官能度。接下来，通过制造相应的填充床微反应器（耐压不锈钢塔），在连续流动条件下评估了AAS非均相催化的有效性。已经证明，共价固定在二氧化硅载体上和流动方式协同作用有助于随着时间的流逝保持酶的活性，从而使得所制备的生物反应器可以长期操作（长达15天）来生产手性靶标。通过umpolung策略。
• Bacillus stearothermophilus acetylacetoin synthase: A new catalyst for C–C bond formation
  作者：Pier Paolo Giovannini、Paola Pedrini、Valentina Venturi、Giancarlo Fantin、Alessandro Medici

  DOI：10.1016/j.molcatb.2010.03.001

  日期：2010.6

  The synthesis of α-hydroxy-1,3-diketones 2 and 3 from the corresponding 1,2-diketones with Bacillus stearothermophilus ATCC2027 acetylacetoin synthase (AAS) was described. The enzyme catalyzed the condensation of the dialkyl- or alkyl-aryl-1,2-diketones 1 with the elimination of a carboxylic acid moiety. The reactions were carried out using either one diketone both acting as donor and acceptor (homo-coupling)

  描述了用嗜热脂肪芽孢杆菌ATCC2027乙酰丙酮合成酶（AAS）从相应的1,2-二酮合成α-羟基-1,3-二酮2和3。该酶催化二烷基-或烷基-芳基-1,2-二酮1的缩合并消除了羧酸部分。使用既充当供体又受主的二酮（均相偶联）或使用两种不同的反应物种（交叉偶联）进行反应。不对称二烷基-1，2-二酮1c – d的均偶联反应提供了区域异构体2（30–42％，ee 67–70％）和3的混合物（19–25％），而使用2,3-丁二酮1a，3,4仅获得1,3-二酮2a（57％），2b（60％）和2e（45％，ee 76％）-己二酮1b和1-苯基-1,2-丙二酮1e。二酮1a和1b以及1b和1e的交叉偶联反应使用不同比例的供体和受体进行。在这两种情况下，唯一的交叉偶联产物是3-乙基-3-羟基-2,4-己二酮4（62％，ee 91％）。
• Enzymatic diastereo- and enantioselective synthesis of α-alkyl-α,β-dihydroxyketones
  作者：Pier Paolo Giovannini、Giancarlo Fantin、Alessandro Massi、Valentina Venturi、Paola Pedrini

  DOI：10.1039/c1ob05928a

  日期：——

  reactions of α-diketones catalyzed by acetylacetoin synthase (AAS) produce a set of α-alkyl-α-hydroxy-β-diketones (30–60%, ee 67–90%), which in turn are reduced regio-, diastereo-, and enantioselectively to the corresponding chiral α-alkyl-α,β-dihydroxyketones (60–70%, ee >95%) using acetylacetoin reductase (AAR) as catalyst. Both enzymes are obtained from Bacillus licheniformis and used in a crude form. The

  报道了制备光学纯的α-烷基-α，β-二羟基酮的酶促策略。α-二酮的均相和交叉偶联反应乙酰丙酮 合酶（AAS）产生一组α-烷基-α-羟基-β-二酮（30-60％，ee 67-90％），进而还原为相应的手性α，区域，非对映体和对映体-烷基-α，β-二羟基酮（60–70％，ee> 95％）使用 乙酰丙酮还原酶（AAR）作为催化剂。两种酶均获自地衣芽孢杆菌，并以粗制形式使用。的相对顺式的对映纯的α，β二羟基产物的立体化学是由NOE实验分配，而它们的绝对构型是由选定的3,4-二羟基-3-甲基-戊-2-酮的天然产物的转化（确定+）-邻苯二酚。
• α-Diketones as acyl anion equivalents: a non-enzymatic thiamine-promoted route to aldehyde–ketone coupling in PEG400 as recyclable medium
  作者：Olga Bortolini、Giancarlo Fantin、Marco Fogagnolo、Pier Paolo Giovannini、Valentina Venturi、Salvatore Pacifico、Alessandro Massi

  DOI：10.1016/j.tet.2011.08.056

  日期：2011.10

  By mimicking the peculiar behavior of thiamine diphosphate-dependent acetylacetoin synthase, it has been demonstrated that thiamine hydrochloride 2a and its simple analogue thiazolium salt 2b are able to activate alpha-diketones as acyl anion equivalents in nucleophilic acylations, such as the homo-coupling of alpha-diketones and the hitherto unreported cross-coupling between a-diketones and alpha-ketoesters. These carboligation reactions were optimized under stoichiometric (2a) and catalytic conditions (2b) by using eco-friendly PEG400 as the reaction medium, thus allowing both solvent and thiazolium salt recycling. (C) 2011 Elsevier Ltd. All rights reserved.