3-(dimethyl(phenyl)silyl)butanoic acid ethyl ester | 67473-43-2

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 脂肪酰基
• 英文名称: 3-(dimethyl(phenyl)silyl)butanoic acid ethyl ester
• 英文别名: ethyl 3-(dimethyl(phenyl)silyl)butanoate；Ethyl 3-[dimethyl(phenyl)silyl]butanoate
• CAS: 67473-43-2
• 化学式: C₁₄H₂₂O₂Si
• 分子量: 250.413
• InChiKey: HKDMVDWVBIDLEO-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.95
• 重原子数：
  17
• 可旋转键数：
  6
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  26.3
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  3-(dimethyl(phenyl)silyl)butanoic acid ethyl ester 在 四丁基氟化铵 、 lithium diisopropyl amide 作用下， 以 四氢呋喃 为溶剂， 反应 4.0h， 生成 反式-2-丁烯酸乙酯
  参考文献：
  名称：

  On the stereochemistry of β-elimination of β-silyl azides

  摘要：

  Fluoride-mediated elimination of syn and anti beta-silyl azides was shown to afford the corresponding (Z)- and (E)-olefins, respectively, demonstrating that beta-elimination of beta-silyl azides is stereospecifically anti. (C) 2003 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/s0040-4039(03)01800-8
• 作为产物：
  描述：

  (E)-ethyl 3-(dimethyl(phenyl)silyl)but-2-enoate 在 C₃₂H₅₀NO₂P*C₈H₁₆*C₃₂H₁₂BF₂₄^(1-)*Ir⁽¹⁺⁾ 、 氢气 作用下， 以 二氯甲烷 为溶剂， 20.0 ℃ 、5.0 MPa 条件下， 反应 4.0h， 以90%的产率得到
  参考文献：
  名称：

  铱催化乙烯基硅烷的对映选择性加氢

  摘要：

  我们已经筛选出了各种各样的手性N，P配体衍生的铱配合物，作为乙烯基硅烷不对称氢化的催化剂，这种转化方法缺乏通常适用的催化剂。从这项研究中出现了几种催化剂，它们能够对带有芳基，烷基，乙氧羰基或羟甲基取代基的三取代或二取代的末端C = C键的乙烯基硅烷进行高度对映选择性氢化。除三甲基甲硅烷基和二甲基（苯基）甲硅烷基衍生物外，三烷氧基甲硅烷基和硅杂环丁基取代的烯烃也用作底物。

  DOI：

  10.1002/adsc.201700162

文献信息

• Bench-Stable Stock Solutions of Silicon Grignard Reagents: Application to Iron- and Cobalt-Catalyzed Radical C(sp³ )-Si Cross-Coupling Reactions
  作者：Weichao Xue、Ryosuke Shishido、Martin Oestreich

  DOI：10.1002/anie.201807640

  日期：2018.9.10

  the preparation of silicon‐based magnesium reagents is reported. The MgBr2 used in the lithium‐to‐magnesium transmetalation step is generated in situ from 1,2‐dibromoethane and elemental magnesium in hot THF. No precipitation of MgBr2 occurs in the heat, and transmetalation at elevated temperature leads to homogeneous stock solutions of the silicon Grignard reagents that are stable and storable in the

  据报道，一种可靠的制备硅基镁试剂的方法。锂到镁的过渡金属化步骤中使用的MgBr 2是由1,2-二溴乙烷和元素镁在热THF中原位生成的。加热过程中不会发生MgBr 2的沉淀，并且在高温下的金属转移会导致硅格氏试剂的均质储备溶液，该溶液在冰箱中稳定且可储存。该方法避免了制备硅原核试剂，例如Si-Si和Si-B试剂。新的格氏试剂被用于前所未有的铁和钴催化的未活化烷基溴的交叉偶联反应。这些镁试剂的官能团耐受性极佳。
• The conjugate addition of a silyl group to enones and its removal with copper(<scp>II</scp>) bromide: a protecting group for the αβ-unsaturation of αβ-unsaturated ketones
  作者：David J. Ager、Ian Fleming、Shailesh K. Patel

  DOI：10.1039/p19810002520

  日期：——

  copper(I) salts react with enones, including esters and aldehydes, to give β-silyl carbonyl compounds in good yield. The β-silylketones can be used in synthesis without risk to the silyl group and the enone group can be restored by bromination-desilylbromination with copper(II) bromide. The principle is illustrated with syntheses of carvone and dihydrojasmone.

  与铜（I）盐混合的甲硅烷基锂试剂与烯酮（包括酯和醛）反应，以高收率得到β-甲硅烷基羰基化合物。β-甲硅烷基酮可用于合成而没有甲硅烷基基团的风险，并且烯酮基团可通过用溴化铜（II）进行溴化-脱甲硅烷基溴化来恢复。香芹酮和二氢茉莉酮的合成说明了该原理。
• Conjugate Additions of a Simple Monosilylcopper Reagent with Use of the CuI·DMS Complex:  Stereoselectivities and a Dramatic Impact by DMS
  作者：Jesse Dambacher、Mikael Bergdahl

  DOI：10.1021/jo048269e

  日期：2005.1.1

  reagent with DMS as the solvent is very useful with sterically hindered (β,β-disubstituted) enones, and provides very high yields of the β-silylated 1,4-addition products. Since there is no oligomerization problem associated with the simple monosilylcuprate reagent, this reagent should be considered as a very useful 1,4-silyl donor to enals, enones, and enoates in conjugate addition reactions.

  描述了利用简单的单甲硅烷基铜酸盐试剂Li [PhMe 2 SiCuI]与α，β-不饱和羰基化合物进行共轭加成。作为（CuI）4（DMS）3配合物的组分或添加的溶剂，二甲基硫醚（DMS）的存在对其化学收率和非对映体比率（dr）的水平都具有惊人的影响。产品。吉尔曼型甲硅烷基氰基甲酸酯Li（Ph 2 MeSi）2 Cu / LiCN}先前已被用来保证在共轭加成反应中获得良好的结果。与简单的Li [PhMe 2]结合使用时，不需要外部添加剂，例如HMPA，三丁基膦或二烷基锌SiCuI]试剂。已经证明，以DMS为溶剂的单甲硅烷基铜酸盐试剂与空间受阻的（β，β-二取代的）烯酮非常有用，并且提供非常高产率的β-甲硅烷基化的1，4-加成产物。由于不存在与简单的单甲硅烷基铜酸酯试剂相关的低聚问题，因此该试剂应被认为是共轭加成反应中烯，烯酮和烯酸酯的非常有用的1,4-甲硅烷基供体。
• Employing the simple monosilylcopper reagent, Li[PhMe₂SiCuI], in 1,4-addition reactions
  作者：Jesse Dambacher、Mikael Bergdahl

  DOI：10.1039/b210792a

  日期：——

  Conjugate addition reactions using the simple Li[PhMe2SiCuI] reagent to a variety of α,β-unsaturated carbonyl compounds is described; dimethyl sulfide from the purification of CuI plays a key role for very high yields as well as high stereoselectivities in the formation of β-silyl carbonyl compounds.

  本文描述了使用简单的Li[PhMe2SiCuI]试剂对多种α,β-不饱和羰基化合物进行的共轭加成反应；从CuI的纯化过程中得到的二甲基硫化物在形成β-硅基羰基化合物时对于获得非常高的产率和高的立体选择性起着关键作用。
• 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。