4-hydroxy-5,5-dimethylhexan-3-one | 88522-71-8

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 4-hydroxy-5,5-dimethylhexan-3-one
• 英文别名: 4-hydroxy-5,5-dimethyl-hexan-3-one
• CAS: 88522-71-8
• 化学式: C₈H₁₆O₂
• 分子量: 144.214
• InChiKey: JSLPVOWQFXBZJF-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.5
• 重原子数：
  10
• 可旋转键数：
  3
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.88
• 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-5,5-dimethylhexan-3-one 生成 (1R,2R,4R)-1-hydroxy-2,5,5-trimethyl-1-phenyl-4-trimethylsilyloxyhexan-3-one
  参考文献：
  名称：

  Acyclic stereoselection. 6. A reagent for achieving high 1,2-diastereoselection in the aldol conversion of chiral aldehydes into 3-hydroxy-2-methylcarboxylic acids

  摘要：

  DOI：

  10.1021/ja00517a056
• 作为产物：
  描述：

  2-羟基-3,3-二甲基丁酸 生成 4-hydroxy-5,5-dimethylhexan-3-one
  参考文献：
  名称：

  Protocols for the preparation of each of the four possible stereoisomeric .alpha.-alkyl-.beta.-hydroxy carboxylic acids from a single chiral aldol reagent

  摘要：

  Protocols have been devised whereby all four possible stereoisomeric alpha-alkyl-beta-hydroxy carboxylic acids can be derived from a single aldol reagent, hydroxy ketone 3. Compound 3, obtained in enantiomerically homogeneous form in 50% overall yield from tert-butylglycine (1), is used for aldol reactions in the form of its trimethylsilyl and tert-butyldimethylsilyl derivatives, 4 and 5. The Z lithium and Z boron enolates of 4 react with various aldehydes to give aldols 8 and 9, respectively. Deprotonation of 4 by bromomagnesium 2,2,6,6-tetramethylpiperidide (MTMP) gives the E enolate, which may be trapped by trimethylsilyl chloride to obtain the E silyl enol ether 11. The E bromomagnesium enolate of 4 reacts with aldehydes to give aldols of structure 15. Transmetalation of the bromomagnesium enolate of keto ether 5 is accomplished by reaction with (triisopropoxy)titanium chloride. The resulting E (triisopropoxy)titanium enolate reacts with aldehydes to provide aldols of structure 17. The aldols resulting from the foregoing reactions are hydrolyzed to keto diols 19-22, which are oxidized to the stereoisomeric alpha-methyl-beta-hydroxy carboxylic acids 23-26.

  DOI：

  10.1021/jo00007a043

文献信息

• Enzymatic Cross‐Benzoin‐Type Condensation of Aliphatic Aldehydes: Enantioselective Synthesis of 1‐Alkyl‐1‐hydroxypropan‐2‐ones and 1‐Alkyl‐1‐hydroxybutan‐2‐ones
  作者：Graziano Di Carmine、Olga Bortolini、Alessandro Massi、Michael Müller、Giovanni Bernacchia、Giancarlo Fantin、Daniele Ragno、Pier Paolo Giovannini

  DOI：10.1002/adsc.201800357

  日期：2018.11.5

  with high conversions (89–99%) and in good to high enantiomeric excess (72–99% ee). In a similar way, high conversions (75–99%) and good ee (76–99%) were observed in reactions performed with the same set of aldehyde acceptors, but using 4‐hydroxy‐4‐methylhexan‐3‐one as propionyl anion donor. This is the first time that most of the products described herein have been prepared via benzoin‐type condensation

  苯甲素类反应已被广泛用作制备α的合成策略-羟基酮。硫胺二磷酸（ThDP）依赖性酶是此类反应类型的不对称形式的出色催化剂。特别是，在芳族反应物的交叉安息香缩合和芳族/脂肪族混合反应中，这些酶的使用导致了高水平的化学，区域和立体选择性。目前的工作证实了脂族反应物的这一趋势，概述了由ThDP依赖性乙酰丙酮：二氯苯酚吲哚酚氧化还原酶（Ao： DCPIP OR）。在这些反应中，使用3-羟基-3-甲基丁-2-酮（甲基乙酰丁）作为活化的乙醛供体，而4-羟基-4-甲基己基-3-酮是首次用作活化丙醛的前体。除了3-羟基戊烷-2-酮和3-羟基己酮-2-酮分别通过甲基乙酰丙酮分别与丙醛和丁醛缩合而得到外消旋形式外，所有其他产物均是通过使用同一供体进行反应而获得的较高的转化率（89–99％）和对映异构体过量至较高的对映体（72–99％）获得了具有更多受阻醛受体的化合物ee）。以类似的方式，在使用相同的一组醛受体但
• Steric influence of silyl groups in titanium- and lithium-mediated aldol condensations
  作者：Chitchanun Panyachotipun、Edward R. Thornton

  DOI：10.1016/s0040-4039(00)98013-4

  日期：——

  Reactions of lithium enolates of α-silyloxyketones 1a, 1b, 2a, and 2b with benzaldehyde yield opposite diastereoselection depending upon the size of the silyl group, but all four titanium enolates lead to high diastereofacial selectivities. These results implicate a nonchelated transition structure which is insensitive to the steric size of the silyl group for the titanium-mediated aldol reactions

  α-甲硅烷基氧酮1a，1b，2a和2b的烯醇锂与苯甲醛的反应根据甲硅烷基的大小而产生相反的非对映选择性，但是所有四个钛烯醇盐均导致非对映选择性高。这些结果暗示了非螯合的过渡结构，其对于钛介导的醛醇缩合反应对甲硅烷基的空间大小不敏感。酮1a对两种相对的顺式加合物（与钛为99：1；与锂为10:90）具有较高的选择性。因为它很容易以单手性形式制备，所以根据需要，1a可以作为制备任何一种产物立体化学的手性前体提供优势。
• Acyclic stereoselection. 12. Double stereodifferentiation with mutual kinetic resolution. A superior class of reagents for control of Cram's rule stereoselection in synthesis of erythro-.alpha.-alkyl-.beta.-hydroxy carboxylic acids from chiral aldehydes
  作者：Clayton H. Heathcock、Michael C. Pirrung、John Lampe、Charles T. Buse、Steven D. Young

  DOI：10.1021/jo00324a017

  日期：1981.5
• Addition of Grignard reagents to O-trimethylsulylated cyanohydrins: Synthesis of acyloins
  作者：Larry R. Krepski、Steven M. Heilmann、Jerald K. Rasmussen

  DOI：10.1016/s0040-4039(00)88265-9

  日期：1983.1
• Alkylation-reduction of carbonyl systems. Part 14. Tandem alkylation-reduction. Highly stereoselective synthesis of (E)-1-hydroxymethyl methyl propenyl ethers from aldehydes using 1-lithio-1-methoxyallene
  作者：Franz J. Weiberth、Stan S. Hall

  DOI：10.1021/jo00225a061

  日期：1985.12