(1S*,3R*)-4-Methyl-1-phenylpentane-1,3-diol | 103668-49-1

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: (1S*,3R*)-4-Methyl-1-phenylpentane-1,3-diol
• 英文别名: 1-phenyl-4-methylpentane-1,3-diol；4-methyl-1-phenylpentane-1,3-diol；(1R,3S)-4-methyl-1-phenylpentane-1,3-diol
• CAS: 103668-49-1
• 化学式: C₁₂H₁₈O₂
• 分子量: 194.274
• InChiKey: UWPRWQABFOJVSG-NWDGAFQWSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.1
• 重原子数：
  14
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  40.5
• 氢给体数：
  2
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  (1S*,3R*)-4-Methyl-1-phenylpentane-1,3-diol 在 六甲基磷酰三胺 、 4-二甲氨基吡啶 、 三乙胺 作用下， 以 四氢呋喃 、 正己烷 、 N,N-二甲基甲酰胺 为溶剂， 反应 1.0h， 生成
  参考文献：
  名称：

  Regioselective Ring Opening of Di-isopropylsilylenes Derived from 1,3-Diols with Alkyl Lithium Reagents

  摘要：

  The selective alkyl lithium-induced ring opening of 1,3-di-isopropylsilylenes is described. The reaction affords a differentially substituted 1,3-diol bearing a silane that resides at the oxygen in the more sterically demanding position. The reaction can be highly selective with a regiochemical preference up to >50:1 and likely proceeds via an alkoxy-silane intermediate. This intermediate can by trapped by methyl iodide to provide the corresponding silyl methyl ether, wherein the silane again resides at the oxygen in the more sterically demanding position.

  DOI：

  10.1021/acs.orglett.5b02529
• 作为产物：
  描述：

  3-hydroxy-4-methyl-1-phenylpentan-1-one 在 二乙基甲氧基硼烷 、 sodium tetrahydroborate 作用下， 以 四氢呋喃 、 甲醇 为溶剂， 以56%的产率得到(1S*,3R*)-4-Methyl-1-phenylpentane-1,3-diol
  参考文献：
  名称：

  Stereospecific conversion of (1R*,3S*)- and (1R*,3R*)-3-cyclohexyl-1-phenylpropane-1,3-diol into the corresponding 2,4-disubstituted oxetanes

  摘要：

  将两个非对映异构体1,3-二醇（3-环己基-1-苯基丙烯-1,3-二醇）转化为邻醇酯，随后用溴乙酸酯处理。在苯基取代位点实现了完全的构型反转，得到了1,3-溴乙酸酯（乙酸3-溴-1-环己基-3-苯基丙基酯）。对溴乙酸酯进行甲醇解后，再进行环闭合，导致在苯基取代位点发生第二次构型反转，最终得到相应的氧环丁烷，并整体保留了构型。

  DOI：

  10.1039/a909163g

文献信息

• Synthesis of<i>anti</i>-1,3-Diols through RuCl₃/PPh₃-Mediated Hydrogenation of β-Hydroxy Ketones: An Alternative to Organoboron Reagents
  作者：Christophe Roche、Olivier Labeeuw、Mansour Haddad、Tahar Ayad、Jean-Pierre Genet、Virginie Ratovelomanana-Vidal、Phannarath Phansavath

  DOI：10.1002/ejoc.200900316

  日期：2009.8

  Hydrogenation of enantioenriched β-hydroxy ketones promoted by the catalyst generated in situ from commercially available and inexpensive RuCl3 and PPh3 under hydrogen pressure allowed the efficient preparation of a variety of anti-1,3-diols in good yields and with a high level of diastereoselectivity. This method should be an interesting alternative to organoboron reagents for the diastereoselective

  在氢气压力下，由市售且廉价的 RuCl3 和 PPh3 原位生成的催化剂促进对映体富集的 β-羟基酮的氢化允许以良好的收率和高水平的非对映选择性有效制备各种抗 1,3-二醇. 这种方法应该是一种有趣的替代有机硼试剂用于 β-羟基酮的非对映选择性还原。(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009)
• Stereospecific conversion of (1R*,3S*)- and (1R*,3R*)-3-cyclohexyl-1-phenylpropane-1,3-diol into the corresponding 2,4-disubstituted oxetanes
  作者：Tajassus Aftab、Christabel Carter、Martin Christlieb、Jennifer Hart、Adam Nelson

  DOI：10.1039/a909163g

  日期：——

  Conversion of two diastereoisomeric 1,3-diols (3-cyclohexyl-1-phenylpropane-1,3-diol) into orthoesters was followed by treatment with acetyl bromide. The 1,3-bromo acetates (acetic acid 3-bromo-1-cyclohexyl-3-phenylpropyl esters) were obtained with complete inversion of configuration at a benzylic site. Methanolysis of the bromo acetates, followed by ring-closure, resulted in a second inversion of configuration at a benzylic site to give the corresponding oxetanes with overall retention of configuration.

  将两个非对映异构体1,3-二醇（3-环己基-1-苯基丙烯-1,3-二醇）转化为邻醇酯，随后用溴乙酸酯处理。在苯基取代位点实现了完全的构型反转，得到了1,3-溴乙酸酯（乙酸3-溴-1-环己基-3-苯基丙基酯）。对溴乙酸酯进行甲醇解后，再进行环闭合，导致在苯基取代位点发生第二次构型反转，最终得到相应的氧环丁烷，并整体保留了构型。
• 1,3-syn diastereoselective reduction of β-hydroxyketones with diisobutylaluminum hydride and tributyltin hydride
  作者：Syun-ichi Kiyooka、Hisanori Kuroda、Yayoi Shimasaki

  DOI：10.1016/s0040-4039(00)84703-6

  日期：1986.1

  1,3-Syn diastereofacial selectivity (>12 : 1) has been achieved in a facile reduction of β-hydroxyketones with DIBAL-H. Tributyltin hydride also has shown 1,3-syn selectivity.

  用DIBAL-H轻松还原β-羟基酮可实现1,3-Syn非对映选择性（> 12：1）。氢化三丁基锡也显示出1,3-syn选择性。
• Stereocontrol in intramolecular hydrosilylation of allyl and homoallyl alcohols: a new approach to the stereoselective synthesis of 1,3-diol skeletons
  作者：Kohei. Tamao、Takashi. Nakajima、Ritsuo. Sumiya、Hitoshi. Arai、Noriko. Higuchi、Yoshihiko. Ito

  DOI：10.1021/ja00279a097

  日期：1986.9

  31.30; H, 5.22; N, 36.52. Found: C, 31.34; H, 5.25; N, 36.70. Low-resolution mass spectral analysis showed the expected molecular ion at m / e 345. The infrared spectrum contained a cyano stretching peak at 2180 cm-'. The 31P NMR spectrum consisted of a singlet at -7.8 ppm. Crystals suitable for X-ray analysis were grown by slow evaporation of a solution of 2 in hexane. The structure of 2 is illustrated

  31.30; H，5.22；N，36.52。发现：C，31.34；H，5.25；N，36.70。低分辨率质谱分析显示预期的分子离子位于 m/e 345。红外光谱在 2180 cm-' 处包含一个氰基拉伸峰。31P NMR 光谱由-7.8 ppm 的单峰组成。通过缓慢蒸发 2 在己烷中的溶液来生长适用于 X 射线分析的晶体。2 的结构如图 2 所示，重要的结构参数在表 I.9 中给出。这两种化合物 1 和 2 与大气接触时稳定，加热至中等温度时不受影响。1和2的X射线结构信息与氰基而不是异氰基排列一致，1°，红外光谱证实了这一点。” 2中氰基的三键比1中的略长,
• 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。