3,3-二甲氧基丁酸甲酯 | 29267-46-7

• 分子结构分类: 有机化合物 - 有机氧化合物
• 中文名称: 3,3-二甲氧基丁酸甲酯
• 英文名称: methyl 3,3-di(methoxy)butanoate
• 英文别名: Dimethyl acetal of methyl 3-oxobutanoate；3,3-bismethoxybutyric acid methyl ester；Methyl 3,3-dimethoxybutanoate
• CAS: 29267-46-7
• 化学式: C₇H₁₄O₄
• 分子量: 162.186
• InChiKey: LSORHVPHSFBPRZ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.1
• 重原子数：
  11
• 可旋转键数：
  5
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.86
• 拓扑面积：
  44.8
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  3,3-二甲氧基丁酸甲酯 在 lithium aluminium tetrahydride 作用下， 以 四氢呋喃 为溶剂， 生成 3,3-dimethoxybutan-1-ol
  参考文献：
  名称：

  走向蛇绿苷a的合成：片段的合成和偶联研究。

  摘要：

  [反应：请参阅文字]对应于C（12）-C（19），C（7）-C（11）和C（1）-C（6）的结构单元3、4和5的不对称合成）报告了蛇绿苷A的片段，以及针对这种微管稳定大环内酯的完整碳骨架组装的硼介导的羟醛偶联研究。

  DOI：

  10.1021/ol034035q
• 作为产物：
  描述：

  乙酰乙酸乙酯 在 <(-)-2,2'-bis(diphenylphosphino)-3,3'-bibenzothiophene>RuCl2 、 氢气 作用下， 以 甲醇 为溶剂， 70.0 ℃ 、9.81 MPa 条件下， 反应 2.0h， 以5%的产率得到3,3-二甲氧基丁酸甲酯
  参考文献：
  名称：

  高效过渡金属催化的立体选择反应的新一类手性二膦配体：双（二苯基膦基）五元双杂芳基。

  摘要：

  描述和合成的新型三类手性（C（2））阻转异构二膦的三个例子，其特征是两个相互连接的五元杂芳族环，阻碍了围绕肛门间键的旋转。光学纯的（+）-和（-）-2,2'-双（二苯基膦基）-4,4'，6,6'-四甲基-3,3'-联苯并[b]噻吩（tetraMe-bitianp）（1a ）和未取代的母体系统（+）-和（-）-双键（1b）。发现它们在100℃下具有光学稳定性，并已成功地用作配体用于Ru（II）催化的α-和β-氧代酯氢化为相应的α-和β-羟基酯以及烯烃的氢化基材。光学和化学产率与在相同实验条件下进行的相同Ru（II）-binap催化反应报道的产率相当。发现2,2'-双（二苯基膦基）-3,3'-联苯并[b]呋喃（1c）（双酚的氧化类似物）在室温下构型不稳定。据报道1a-c的Pd复合物的完整结构X射线阐明。讨论了这些双杂芳族配体相对于经典联芳基体系的优势。

  DOI：

  10.1021/jo960211f

文献信息

• Asymmetric hydrogenation of prochiral carboxylic acids and functionalized carbonyl compounds catalysed by ruthenium(II)-binap complexes with aryl nitriles (binap = (R)- or (S)-2,2′-bis(diphenylphosphino)-1,1′-binaphthyl)
  作者：Liming Shao、Kasumi Takeuchi、Makoto Ikemoto、Toshiyasu Kawai、Masamichi Ogasawara、Hiroshi Takeuchi、Hiroyuki Kawano、Masahiko Saburi

  DOI：10.1016/0022-328x(92)83466-u

  日期：1992.2

  Complexes RuCl2(ArCN)2(binap), II (binap = (R)- or (S)-2,2′-bis(diphenylphosphino)- 1,1′-binaphthyl; ArCN = benzonitrile, a; 2-furancarbonitrile, b; pentafluorobenzonitrile, c) were prepared, and their solution properties were investigated by 31P NMR measurements. The catalytic activities and enantioselectivities for IIa–c catalysed hydrogenation of some prochiral acids were very similar to those provided

  配合物RuCl 2（ArCN）2（binap），II（binap =（R）-或（S）-2,2'-双（二苯基膦基）-1,1'-联萘基; ArCN =苄腈，a; 2-呋喃腈； b；五氟苄腈，c）被制备，并且它们的溶液性质通过31 P NMR测量来研究。IIa–c催化某些手性酸的氢化反应的催化活性和对映选择性与Ru 2 Cl 4（binap）2（NEt 3）提供的催化活性和对映选择性非常相似。），I。然而，在β-官能化羰基化合物的氢化中，IIa–c与复合物I相比，活性和/或选择性大大降低。 II中的ArCN。
• Synthesis of new cationic BINAP–ruthenium(<scp>II</scp>) complexes and their use in asymmetric hydrogenation [BINAP = 2,2′-bis(diphenylphosphino)-1,1′-binaphthyl]
  作者：Kazushi Mashima、Koh-hei Kusano、Tetsuo Ohta、Ryoji Noyori、Hidemasa Takaya

  DOI：10.1039/c39890001208

  日期：——

  [RuX2(arene)]2(1) and (S)-BINAP gives cationic BINAP–ruthenium complexes of the formula RuX(arene)[(S)-binap]} Y (2)(X = Cl, Br, and l; Y = Cl, Br, l, BF4, and BPh4; arene = C6H6 and p-MeC6H4CHMe2) which are efficient catalyst precursors for enantioselective hydrogenation of various prochiral alkenic and ketonic substrates [BINAP = 2,2′-bis(diphenylphosphino)-1,1′-binaphthyl]; a crystal structure of (2)(with

  [RuX 2（arene）] 2（1）与（S）-BINAP的反应产生式为RuX（arene）[（S）-binap]} Y（2）（X = Cl， Br和l； Y = Cl，Br，l，BF 4和BPh 4；芳烃= C 6 H 6和p -MeC 6 H 4 CHMe 2），它们是对各种手性烯键和酮键进行对映选择性氢化的有效催化剂前体底物[BINAP ＝ 2，2′-双（二苯基膦基）-1，1′-联萘基]；（2）（X = Cl，Y = BF 4的晶体结构）。
• An Efficient and Versatile Procedure for the Synthesis of Acetals from ­Aldehydes and Ketones Catalyzed by Lithium Tetrafluoroborate
  作者：Tsuneo Sato、Nao Hamada、Kiyoshi Kazahaya、Hisashi Shimizu

  DOI：10.1055/s-2004-820038

  日期：——

  Acetals are obtained in good to excellent yields by treatment of aldehydes and ketones with trialkyl orthoformate and the corresponding alcohol in the presence of a catalytic amount of lithium tetrafluoroborate. Due to the mild reaction conditions, this method is compatible with acid-sensitive substrates.

  在催化量的四氟硼酸锂存在下，用原甲酸三烷基酯和相应的醇处理醛和酮，以良好至极好的收率获得缩醛。由于反应条件温和，该方法适用于对酸敏感的底物。
• Cationic BINAP-Ru(II) Halide Complexes: Highly Efficient Catalysts for Stereoselective Asymmetric Hydrogenation of .alpha.- and .beta.-Functionalized Ketones
  作者：Kazushi Mashima、Koh-hei Kusano、Naomasa Sato、Yoh-ichi Matsumura、Kyoko Nozaki、Hidenori Kumobayashi、Noboru Sayo、Yoji Hori、Takero Ishizaki

  DOI：10.1021/jo00090a026

  日期：1994.6

  Cationic ruthenium-BINAP complexes 5, 7, and 10 of the formula [RuX((S)-BINAP) (arene)]Y, where X = Cl, Br, I; Y = Cl, Br, I, BF4, B(C6H5)(4); arene = benzene, p-cymene, ethyl benzoate, and their enantiomers have been prepared by the reaction of arene-ruthenium halide complexes 4, 6, and 9 with (S)-BINAP or (R)-BINAP. Structures of the complexes were established by spectroscopy, conductivity, and a single-crystal X-ray analysis (5d: orthorhombic, P2(1)2(1)2; a 20.141(2) Angstrom, b = 18.504(1) Angstrom, c 12.241(1) Angstrom V = 4562.0(7) Angstrom(3), Z = 4, R = 0.078 for unique 4177 reflections). BINAP derivatives with various substituents at the para and meta positions of four phenyl rings on phosphorus atoms and their cationic Ru(II) complexes have also been synthesized. These BINAP-Ru(II) complexes have been used as catalysts for the asymmetric hydrogenation of various unsaturated organic compounds such as alpha- and beta-keto esters, allylic alcohols, and alpha,beta-unsaturated carboxylic acids in excellent diastereo- and/or enantioselectivities. Catalytic activities and stereoselectivities depend highly on reaction conditions such as solvent, temperature, and additives. Variation of halogen ligands bound to ruthenium atom and substituents on four phenyl rings of BINAP also have exerted remarkable effects on the efficiency of the catalysis. Asymmetric hydrogenation of methyl (+/-)-2-(benzamidomethyl)-3-oxobutanoate catalyzed by the species derived from 9c and 3,5((t)Bu)(2)-BINAP afforded the corresponding syn-(2S,3R)-17 in 98% de and 99% ee.
• Synthesis and characterization of mono- and tri-nuclear ruthenium complexes of 2,2′-bis(diphenylphosphino)-1,1′-binaphthyl and their catalytic activity
  作者：Kazushi Mashima、Takahiro Hino、Hidemasa Takaya

  DOI：10.1039/dt9920002099

  日期：——

  The structures of ruthenium(II) complexes formed in solution from [RuX(S)-binap}(arene)]Y (S)-3 (X, Y = halide and/or BF4-; binap = 2,2'-bis(diphenylphosphino)-1,1'-binaphthyl; arene = benzene or p-cymene) depend on the solvent. In acetonitrile-methanol (1 : 1 dicationic complexes [Ru(S)-binap}(MeCN)4]X(Y) (S)-4 (X = Y = Cl a; X = Cl, Y = BF4 b; X = Y = Br c; or X = Y = I d) are predominantly formed, while monocationic species [RuX(S)-binap}(MeCN)3]X (S)-6 (X = Cl a, Br b or I c) were observed in acetonitrile. These mono- and di-cationic species could not be isolated pure, while [RuCl2(S)-binap}(MeCN)2] (S)-5 was isolated from (S)-4a or (S)-6a upon concentration of the reaction mixture. In methanol without donor molecules such as acetonitrile, cationic trinuclear complexes [Ru3X5(S)-binap}3]Y (S)-7 (X = Y = Cl a; X = Cl, Y = BF4 b or X = Y = Br c) were exclusively formed by heating at 60-degrees-C or UV irradiation of a solution of (S)-3. The structure of (S)-7 was characterized by spectral data and an X-ray crystallographic analysis of (S)-7b [orthorhombic, space group P2(1)2(1)2(1), a = 26.328(5), b = 18.140(3), c = 26.374(4), Z = 4, R' = 0.083]. The relationship between the structure of the Ru(II)(binap) complexes and their catalytic activities for asymmetric hydrogenation of methyl 3-oxobutanoate has been investigated.