methyl 3-[(dimethyl)phenylsilyl]propionate | 59344-04-6

• 分子结构分类: 有机化合物 - 有机金属化合物 - 有机类金属化合物
• 英文名称: methyl 3-[(dimethyl)phenylsilyl]propionate
• 英文别名: Methyl 3-dimethyl(phenyl)silylpropanoate；Methyl 3-[dimethyl(phenyl)silyl]propanoate
• CAS: 59344-04-6
• 化学式: C₁₂H₁₈O₂Si
• 分子量: 222.359
• InChiKey: MPKMHCNCUAAGQP-UHFFFAOYSA-N

物化性质

• 沸点：
  287.0±23.0 °C(Predicted)
• 密度：
  1.4950 g/cm3(Temp: 25 °C)

计算性质

• 辛醇/水分配系数(LogP)：
  2.17
• 重原子数：
  15
• 可旋转键数：
  5
• 环数：
  1.0
• 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

• 作为反应物：
  描述：

  methyl 3-[(dimethyl)phenylsilyl]propionate 在 platinum(IV) oxide lithium hydroxide 、 N-溴代丁二酰亚胺(NBS) 、 正丁基锂 、 N,N,N',N'-tetramethylguanidinium azide 、 氢气 、 sodium hydride 、 N,N-二异丙基乙胺 作用下， 以 四氢呋喃 、 乙醇 、 正己烷 、 二氯甲烷 、 水 、 乙腈 为溶剂， 反应 34.5h， 生成 (R)-2-azido-3-[(dimethyl)phenylsilyl]propionic acid
  参考文献：
  名称：

  Enzymatic synthesis of enantiomerically enriched d- and l-3-silylated alanines by deracemization of dl-5-silylmethylated hydantoins

  摘要：

  The hydantoinase process was shown to be extendable to the production of highly lipophilic, silicon-containing amino acids. Two hydantoinases of different origin and stereoselectivities and one L-N-carbamoylase were used for the highly stereoselective bioconversion of (dimethyl)phenylsilyl- and 1-methyl-1-silacyclopentyl substituted alanine derivatives. The enantiomeric purities and absolute configuration of the products were determined with reference compounds that were synthesized with the aid of the Evans oxazolidinone auxiliary. (C) 2001 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0957-4166(01)00028-3
• 作为产物：
  描述：

  苯基二甲基氯硅烷 在 sodium hydroxide 、 臭氧 、 magnesium 作用下， 以 乙醚 、 二氯甲烷 为溶剂， 反应 72.5h， 生成 methyl 3-[(dimethyl)phenylsilyl]propionate
  参考文献：
  名称：

  Enzymatic synthesis of enantiomerically enriched d- and l-3-silylated alanines by deracemization of dl-5-silylmethylated hydantoins

  摘要：

  The hydantoinase process was shown to be extendable to the production of highly lipophilic, silicon-containing amino acids. Two hydantoinases of different origin and stereoselectivities and one L-N-carbamoylase were used for the highly stereoselective bioconversion of (dimethyl)phenylsilyl- and 1-methyl-1-silacyclopentyl substituted alanine derivatives. The enantiomeric purities and absolute configuration of the products were determined with reference compounds that were synthesized with the aid of the Evans oxazolidinone auxiliary. (C) 2001 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0957-4166(01)00028-3

文献信息

• Conjugate addition of silyl groups to β-unsubstituted enones, & Si-to-OH conversion: a synthesis of (±)-lavandulol
  作者：Ian Fleming、Duckhee Lee

  DOI：10.1016/0040-4039(96)01519-5

  日期：1996.9

  TMS chloride raises the yield in the conjugate addition of silylcuprates and zincates to β-unsubstituted enones, and Si-to-OH conversion is possible using the 2-methylbut-2-enyl(diphenyl)silyl group in the presence of highly nucleophilic alkenes. Both reactions are used in a synthesis of lavandulol.

  TMS氯化物可提高甲硅烷基铜酸酯和锌酸酯与β-未取代烯酮的共轭加成反应的收率，在高度亲核性烯烃存在的情况下，使用2-甲基丁-2-烯基（二苯基）甲硅烷基可实现Si-OH的转化。两种反应都用于合成拉维度洛。
• Hydrosilylation of α,β-unsaturated nitriles and esters catalyzed by tris (triphenylphosphine)chlororhodium
  作者：Iwao Ojima、Miyoko Kumagai、Yoichiro Nagai

  DOI：10.1016/s0022-328x(00)87057-6

  日期：1976.5

  trichlorosilane which afforded β-adduct with acrylonitrile. On the other hand, the hydrosilylation of α,β-unsaturated esters gave rather complex results. The selectivity of the reactions was dramatically affected by the substituent of the ester group and that on the β-carbon. Thus, the hydrosilylation of ethyl acrylate with triethylsilane afforded a β-adduct, but, that of ethyl crotonate using the same hydrosilane

  描述了使用三（三苯基膦）氯铑作为催化剂的α，β-不饱和腈和酯的氢化硅烷化，例如丙烯腈，巴豆腈，肉桂腈，丙烯酸乙酯和甲基丙烯酸酯，巴豆酸乙酯和甲基丙烯酸甲酯以及甲基丙烯酸乙酯和甲基丙烯酸甲酯。α，β-不饱和腈的氢化硅烷化仅以高收率提供α-加合物，除了三氯硅烷的情况下，其提供了带有丙烯腈的β-加合物。另一方面，α，β-不饱和酯的氢化硅烷化产生相当复杂的结果。反应的选择性受酯基的取代基和β-碳上的取代基的影响很大。因此，丙烯酸乙酯与三乙基硅烷的氢化硅烷化得到β-加合物，但是使用相同的氢化硅烷的巴豆酸乙酯的氢化硅烷化仅得到1,4-加合物。
• New functional allylic lithium reagents: gem-dialkoxyallyllithium reagents: a useful route to β-silyl- and β-stannylpropionate esters
  作者：Dietmar Seyferth、Robert E. Mammarella、Helmut A. Klein

  DOI：10.1016/s0022-328x(00)90330-9

  日期：1980.7

  -95°C results in formation of gem-dialkoxyallyllithium reagents, Li[CH2CHC(OR)2]. These react with organosilicon and organotin chlorides to give ketene acetals, R3SiCH2CHC(OR)2 and R3SnCH2CHC(OR)2. The acid hydrolysis of these products produces β-substituted propionic acid esters, R3SiCH2CH2CO2R and R3SnCH2CH2CO2R. Reactions of these lithium reagents with allyl bromide gave esters of 5-hexonoic acid,

  仲丁基锂与反应丙烯醛二烷基缩醛的THF或THF / ET 2 O /戊烷在-95℃下导致形成的宝石-dialkoxyallyllithium试剂，锂[CH 2 CHC（OR）2 ]。这些反应用有机硅和有机锡氯化物，得到烯酮缩醛，R 3 SICH 2 CHC（OR）2和R 3 SNCH 2 CHC（OR）2。这些产物的酸水解产生β-取代的丙酸酯，R 3 SiCH 2 CH 2 CO 2 R和R 3 SnCH 2 CH 2CO 2这些锂试剂与烯丙基溴反应R.得到5- hexonoic酸的酯，CH 2 CH（CH 2）3 CO 2 R（R = ME等）。
• Stereocontrol in organic synthesis using silicon-containing compounds. Syntheses of (±)-2-deoxyribonolactone and (±)-arabonolactone
  作者：Ian Fleming、Sunil K. Ghosh

  DOI：10.1039/a804282i

  日期：——

  Samarium iodide reacts with methyl (Z)-3-dimethyl(4-methylphenyl)silylprop-2-enoate 5b to give dimethyl (3RS,4SR)-3,4-bis[dimethyl(4-methylphenyl)silyl]hexane-1,6-dioate 8b with high stereoselectivity. This meso diester can be converted into (3RS,4SR)-3,4-bis[dimethyl(4-methylphenyl)silyl]pentan-5-olide 16 by Dieckmann cyclisation, demethoxycarbonylation and Baeyer–Villiger reaction. Silyl-to-hydroxy

  碘化与（Z）-3-二甲基（4-甲基苯基）甲硅烷基丙-2-烯酸酯5b反应生成二甲基（3 RS，4 SR）-3,4-双[二甲基（4-甲基苯基）甲硅烷基]己烷-具有高立体选择性的1，6-二碘8b。通过Dieckmann环化，脱甲氧基羰基化和Baeyer-Villiger反应，该内消旋二酯可转化为（3 RS，4 SR）-3,4-双[二甲基（4-甲基苯基）甲硅烷基]戊基-5-乙交酯。甲硅烷基到羟基的转化和再内酯化得到（±）-脱氧核糖内酯，抗选择性烯醇盐羟基化，然后甲硅烷基到羟基的转化得到（±）-阿拉伯内酯。尝试合成具有相对构型的糖（3 RS，4 RS）被（3 RS，4 SR）-3,4-双[二[二甲基（4-甲基苯基）甲硅烷基] -5-羟基戊酸28- （3 RS，4 SR）-3,5-双[二甲基（4-甲基苯基）甲硅烷基]戊丹-1,4-乙交酯30。
• Organic Photoredox-Catalyzed Silyl Radical Generation from Silylboronate
  作者：Naho Takemura、Yuto Sumida、Hirohisa Ohmiya

  DOI：10.1021/acscatal.2c01964

  日期：2022.7.1

  A visible-light-driven silyl radical generation method from silylboronates has been developed. The activation of silylboronates with a catalytic amount of mild base promoted the single-electron oxidation process to form silyl radicals. Facile single electron transfer for the borate form readily occurred without hydrogen atom transfer for hydrosilane in the presence of various photoredox catalysts.

  已经开发了一种由甲硅烷基硼酸盐产生可见光驱动的甲硅烷基自由基的方法。用催化量的温和碱活化甲硅烷基硼酸酯促进了单电子氧化过程形成甲硅烷基自由基。在各种光氧化还原催化剂的存在下，硼酸盐形式的简单单电子转移很容易发生，而氢硅烷没有氢原子转移。将该协议与自由基介导的 N-杂环卡宾催化相结合，通过自由基中继过程与甲硅烷基自由基产生，使烯烃的酰基化成为可能。此外，最近用于合成甲硅烷基硼酸盐的先进方法显着提高了这种甲硅烷基自由基生成过程的效用。