(S)-3-[bis(ethoxycarbonyl)methyl]cyclohexenone | 151600-50-9

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羧酸及其衍生物
• 英文名称: (S)-3-[bis(ethoxycarbonyl)methyl]cyclohexenone
• 英文别名: (S)-3-cyclohexenone；(S)-3-cyclohexanone；(S)-3-[bis(ethoxycarbonyl)methyl]cyclohexanone；(-)-diethyl (S)-2-(3-oxocyclohexyl)malonate；(S)-diethyl 2-(3-oxocyclohexyl)malonate；diethyl (S)-2-(3-oxocyclohexyl)malonate；diethyl 2-[(1S)-3-oxocyclohexyl]propanedioate
• CAS: 151600-50-9
• 化学式: C₁₃H₂₀O₅
• 分子量: 256.299
• InChiKey: IKOAYBMYVQZXPV-VIFPVBQESA-N

物化性质

• 沸点：
  338.0±12.0 °C(Predicted)
• 密度：
  1.123±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.5
• 重原子数：
  18
• 可旋转键数：
  7
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.77
• 拓扑面积：
  69.7
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  (S)-3-[bis(ethoxycarbonyl)methyl]cyclohexenone 在 sodium tetrahydroborate 、 盐酸 作用下， 以 乙醇 、 水 为溶剂， 反应 3.0h， 以80%的产率得到(-)-diethyl 2-((1S,3S)-3-hydroxycyclohexyl)malonate
  参考文献：
  名称：

  Chemoenzymatic synthesis of 2-oxabicyclo[3.3.1]nonan-3-one enantiomers via microbial reduction by Absidia coerulea AM 93

  摘要：

  Microbial enantioselective reduction of (+/-)-diethyl 2-(3-oxocyclohexyl)malonate (1) has been described. A screening test oil twenty-four fungi strains was carried Out. Most of the microorganisms preferred bioreduction of (+)-isomer of delta-ketoester (1) to (+)-trans delta-hydroxy ester (2) with the anti-Prelog selectivity. Biotransformation conditions using Absidia coerulea AM 93 were optimized with respect to the growth medium, temperature and pH. An effect of 48 chemical additives oil the Course of biotransformation was checked. (-)-Diethyl 2-((S)-3-oxocyclohexyl)malonate ((-)-1) (ee=98%) and (+)-diethyl 2-((1R, 3R)-3-hydroxycyclohexyl)malonate ((+)-2) (ee=99%)were isolated and subjected to chemical lactonization, leading to (+)-(1R, 5S)-2-oxabicyclo[3.3.1]nonan-3-one ((+)-3) and (-)-(1S, 5R)-2-oxabicyclo[3.3.1]nonan-3-one ((-)-3). The absolute configuration of product (-)-1 was confirmed by comparison of its optical rotation with the literature data. The absolute configuration the carbon atom hearing hydroxyl group in product (+)-2 was determined using the Mosher's ester. (C) 2009 Elsevier B.V. All rights reserved.

  DOI：

  10.1016/j.molcatb.2009.11.005
• 作为产物：
  描述：

  2-环己烯-1-酮 、 丙二酸二乙酯 在 N-[（1S，2S）-2-氨基环己基]-N''-[3,5-双（三氟甲基）苯基]硫脲 、 4-吡咯烷基吡啶 作用下， 以 甲苯 为溶剂， 以94%的产率得到(S)-3-[bis(ethoxycarbonyl)methyl]cyclohexenone
  参考文献：
  名称：

  手性硫脲/PPY双催化剂体系促进丙二酸酯与α,β-不饱和酮的高效不对称迈克尔加成反应

  摘要：

  由手性硫脲和 4-吡咯烷吡啶 (PPY) 在甲苯中组成的组合双催化剂体系有效地促进了丙二酸酯与 α,β-不饱和酮的对映选择性迈克尔加成反应。预期的具有环状和无环烯酮的迈克尔加合物以优异的产率和优异的对映选择性获得。

  DOI：

  10.1055/s-0032-1317317

文献信息

• Synthesis and evaluation of guanidinyl pyrrolidines as bifunctional catalysts for enantioselective conjugate additions to cyclic enones
  作者：Sunil V. Pansare、Rajinikanth Lingampally

  DOI：10.1039/b812038b

  日期：——

  Guanidinyl pyrrolidines derived from ‘S’-proline are effective catalysts for the enantioselective conjugate addition of malonate, nitroalkane and other carbon and heteroatom nucleophiles to cyclohexenone and cyclopentenone in the absence of basic additives. The stereoselectivity is strongly dependant on catalyst loading as well as reaction concentration.

  衍生自“ S ”-脯氨酸的胍基吡咯烷是将丙二酸酯，硝基烷和其他碳原子和杂原子亲核试剂对映选择性共轭加成的有效催化剂。环己烯酮 和 环戊烯酮在没有碱性添加剂的情况下。立体选择性很大程度上取决于催化剂的负载以及反应浓度。
• Effect of Microwaves in the Chiral Switching Asymmetric Michael Reaction
  作者：S. Narasimhan、S. Velmathi

  DOI：10.3390/80200256

  日期：——

  Highly enantioselective Michael reactions of malonates with cyclic enones are achieved in remarkably less time under microwave irradiation using newly developed heterobimetallic catalysts.

  使用新开发的杂双金属催化剂，在微波辐射下，丙二酸酯与环烯酮的高度对映选择性迈克尔反应可在显着更短的时间内实现。
• Lithium bis[(1R,5R)-3-aza-3-benzyl-1,5-diphenylpentan-1,5-diolato]-aluminium — A new heterobimetallic catalyst for Michael addition reactions
  作者：G Manickam、G Sundararajan

  DOI：10.1016/s0040-4020(99)00044-7

  日期：1999.2

  LiAlH4 to give the heterobimetallic complex 2 of the composition [(12-Al)Li]. Complex 2 was characterised by 1H-, 13C-, 27Al- and 7Li-NMR spectral data. Also, 2 when used in catalytic amounts accelerates Michael addition of malonates and thiophenol to α,β-unsaturated compounds like aldehydes, ketones, cyano and nitro compounds with high yield. Asymmetric induction in the Michael adducts has also been

  的c ^ 2 -对称氨基二醇，（1 - [R，5 - [R）-3-氮杂-3-苄基-1,5-二苯基戊-1,5-二醇，1 - [（R，R）-1 ]与发生反应的LiAlH参见图4，得到组成为[（1 2 -Al）Li]的杂双金属配合物2。配合物2的特征在于1 H-，13 C-，27 Al-和7 Li-NMR光谱数据。还有2当以催化量使用时，以高收率促进丙二酸酯和硫酚的迈克尔加成到α，β-不饱和化合物（如醛，酮，氰基和硝基化合物）上。当使用对映体纯的催化剂2时，还观察到迈克尔加合物中的不对称诱导。
• Catalytic Asymmetric Michael Reactions Promoted by a Lithium-Free Lanthanum-BINOL Complex
  作者：Hiroaki Sasai、Takayoshi Arai、Masakatsu Shibasaki

  DOI：10.1021/ja00083a053

  日期：1994.2

  a new lithium-free BINOL-lanthanum complex, which is quite effective in catalytic asymmetric Michael reaction. We have succeeded in developing effective asymmetric base catalysts, in particular, asymmetric ester enolate catalysts for asymmetric Michael reactions. Two asymmetric lanthanum complexes are now available, namely, BINOL-lanthanum-lithium complex, which is quite effective in catalytic asymmetric

  在这篇通讯中，我们报告了一种新的无锂 BINOL-镧络合物，它在催化不对称迈克尔反应中非常有效。我们已成功开发出有效的不对称碱催化剂，特别是用于不对称迈克尔反应的不对称酯烯醇化物催化剂。现在有两种不对称镧配合物，即 BINOL-镧-锂配合物，在催化不对称亚硝基醛反应中非常有效，以及一种新的无锂 BINOL-镧酯烯醇化物配合物，在催化不对称迈克尔反应中非常有效。这两种配合物在催化不对称硝基醛醇和不对称迈克尔反应的能力方面相互补充。14 个参考文献，1 个图，2 个标签。
• Asymmetric organocatalytic conjugate addition of malonates to enones using a proline tetrazole catalyst
  作者：Kristian Rahbek Knudsen、Claire E. T. Mitchell、Steven V. Ley

  DOI：10.1039/b514636d

  日期：——

  5-Pyrrolidin-2-yltetrazole performs as a useful organocatalyst for the asymmetric addition of malonates to a range of enones, with good to excellent enantioselectivities.

  5-吡咯烷-2-基四唑作为有用的有机催化剂，用于丙二酸酯不对称加成到一系列烯酮中，具有良好的至优异的对映选择性。