3-methyl-5-phenyl-5-pentanolide

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 内酯类
• 英文名称: 3-methyl-5-phenyl-5-pentanolide
• 英文别名: (4R,6S)-4-methyl-6-phenyloxan-2-one
• 化学式: C₁₂H₁₄O₂
• 分子量: 190.242
• InChiKey: XBUZDZMHKVZNBP-KOLCDFICSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.5
• 重原子数：
  14
• 可旋转键数：
  1
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.42
• 拓扑面积：
  26.3
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为产物：
  描述：

  在 samarium diiodide 、 Amberlyte IR 120 、 异丙硫醇 作用下， 以 四氢呋喃 、 丙酮 为溶剂， 反应 10.0h， 生成 3-methyl-5-phenyl-5-pentanolide
  参考文献：
  名称：

  通过一锅顺序缩醛化，Tishchenko反应和by离子和硫醇的协同催化内酯化作用，从5-氧代烷醛立体选择性合成δ-内酯。

  摘要：

  通过sa离子和硫醇的协同催化，一系列5-氧代烷醛以有效和立体选择性的方式转化为（取代的）δ-内酯。这一一锅法包括一系列缩醛化，Tishchenko反应和内酯化。与醇相比，有意使用硫醇有利于促进催化循环。提出了反应机理和立体化学，并得到了一些实验证据的支持。sa离子/硫醇共催化反应显示出远程控制的特征，适用于旋光性δ-内酯的不对称合成。这项研究还证明了两种昆虫信息素（2S，5R）-2-甲基己内酯和（R）-十六烷内酯的合成，

  DOI：

  10.1021/jo016058t

文献信息

• In search of open-chain 1,3-stereocontrol
  作者：Asun Barbero、David C. Blakemore、Ian Fleming、Robert N. Wesley

  DOI：10.1039/a607545b

  日期：——

  Methylation of methyl 4-phenylpentanoate 25 gives the diastereoisomers methyl (2RS,4SR )-2-methyl-4-phenylpentanoate 26 and methyl (2RS,4RS)- 2-methyl-4-phenylpentanoate 27 in a ratio of 44∶56. The aldehydes 3-dimethyl(phenyl)silylbutanal 28, 3-dimethyl(phenyl)silyl-3-phenylpropanal 32 and 3-dimethyl(phenyl)silyl-4-methylpentanal 36, each of which has a stereogenic centre on C-3 carrying a silyl group and successively also a methyl, a phenyl and an isopropyl group, react with a range of methyl, phenyl and isopropyl nucleophiles to give pairs of diastereoisomeric secondary alcohols 40–42, 47–49 and 54–56 having 1,3 related stereocentres. The same alcohols 43–45, 50–52 and 57–59 are also prepared by reduction of the corresponding ketones 29–31, 33–35 and 37–39 with a range of hydride reagents, and three of the ketones, 31, 35 and 39, react with phenyllithium to give mixtures of the tertiary alcohols 46, 53 and 60. The (E)- and (Z)-α,β-unsaturated methyl esters, 61, 62, 64, 65, 67 and 68, prepared from the same three aldehydes with methoxycarbonylmethyltriphenylphosphorane, react with the phenyldimethylsilyl-cuprate and -zincate reagents to give diastereoisomeric pairs of 1,3-disilylated esters. Likewise, the α,β-unsaturated dimethyl diesters, 63, 66 and 69, prepared from the same three aldehydes with dimethyl malonate, react with phenyldimethylsilyllithium and the corresponding cuprate and zincate reagents to give diastereoisomeric pairs of 1,3-disilylated diesters, and with various methyl and phenyl nucleophiles to give the corresponding pairs of diastereoisomeric diesters with stereogenic centres at C-3 and C-5. The relative stereochemistry of all but two of the products having 1,3-related stereocentres has been proved by silyl-to-hydroxy conversion using mercuric acetate and peracetic acid to give the corresponding alcohols or their derived lactones.An attempt to identify a purely steric rule by which it might be possible to predict which diastereoisomer would be the major product in each of these reactions was based on arguments about, and molecular mechanics calculations of, the lowest-energy conformations of the starting materials. The only rule that emerges is that ketones are regularly attacked in sense B, defined in the drawings 21 and 23, in a conformation that minimises the interaction between the group M on the stereogenic centre and the group R1 on the other side of the ketone, but even within this group of reactions, phenyl groups in either or both locations sometimes lead to anomalies.Krapcho reactions take place more rapidly and in higher yield using four equivalents of lithium chloride in place of the usual sodium chloride, and adding two equivalents of water to the DMSO.

  将 4-苯基戊酸甲酯 25 甲酯化，得到非对映异构体(2RS,4SR )-2-甲基-4-苯基戊酸甲酯 26 和(2RS,4RS)-2-甲基-4-苯基戊酸甲酯 27，比例为 44∶56。3-二甲基（苯基）硅基丁醛 28、3-二甲基（苯基）硅基-3-苯基丙醛 32 和 3-二甲基（苯基）硅基-4-甲基戊醛 36，每种醛的 C-3 上都有一个带有硅基的立体中心，并先后带有一个甲基、一个苯基和一个异丙基、与一系列的甲基、苯基和异丙基亲核物反应，得到一对非对映异构的仲醇 40-42、47-49 和 54-56，它们具有 1,3 个相关的立体中心。同样的醇 43-45、50-52 和 57-59 也可以通过相应的酮 29-31、33-35 和 37-39 与一系列氢化物试剂发生还原反应来制备，其中三个酮 31、35 和 39 与苯基锂发生反应，得到叔醇 46、53 和 60 的混合物。 (E)-和(Z)-α,β-不饱和甲基酯 61、62、64、65、67 和 68 由相同的三种醛与甲氧羰基甲基三苯基膦制备而成，它们与苯基二甲基硅琥珀酸酯试剂和锌酸试剂反应，得到非对映异构的 1,3-二硅烷化酯对。同样，由相同的三种醛与丙二酸二甲酯制备的 α、β-不饱和二甲基二酯 63、66 和 69 与苯基二甲基硅烷基锂及相应的铜酸盐和锌酸盐试剂发生反应，生成一对非对映异构的 1,3-二硅烷基二酯，与各种甲基和苯基亲核剂发生反应，生成相应的一对非对映异构的二酯，其立体中心位于 C-3 和 C-5。除了两种具有 1,3 相关立体中心的产物外，其他所有产物的相对立体化学性质都已通过使用乙酸巯基和过乙酸进行硅基-羟基转换而得到相应的醇或其衍生内酯得到证实。出现的唯一规则是，酮在图 21 和图 23 中定义的 B 意义上经常被攻击，其构象使立体中心上的基团 M 与酮另一侧的基团 R1 之间的相互作用最小，但即使在这组反应中，苯基在任一位置或两个位置有时也会导致异常。
• Cooperative Catalysis of Samarium Diiodide and Mercaptan in a Stereoselective One-Pot Transformation of 5-Oxopentanals into δ-Lactones
  作者：Jue-Liang Hsu、Chao-Tsen Chen、Jim-Min Fang

  DOI：10.1021/ol9911526

  日期：1999.12.1

  [GRAPHICS]We demonstrate a general method for conversion of various 5-oxopentanals to substituted delta-lactones and 1-oxa-2-decalones by the synergistic catalysis of samarium diiodide and 2-propanethiol (or disulfide), The deliberate use of mercaptan is advantageous to facilitate the catalytic cycle, This method shows high stereoselectivities, and an enantioselective procedure is feasible by using the chiral mercaptan (1R,2S)-1 phenyl-2-(N-acetamido)propanethiol as a promoter.