(R)-methyl-5-oxo-3,5-diphenylpentanoate

• 分子结构分类: 有机化合物 - 木脂素、新木脂素和相关化合物
• 英文名称: (R)-methyl-5-oxo-3,5-diphenylpentanoate
• 英文别名: methyl 5-oxo-3,5-diphenylpentanoate；(R)-3-phenyl-4-benzoylbutyric acid methyl ester；methyl (3R)-5-oxo-3,5-diphenylpentanoate
• 化学式: C₁₈H₁₈O₃
• 分子量: 282.339
• InChiKey: NOXBNKMKZKRHGZ-MRXNPFEDSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.1
• 重原子数：
  21
• 可旋转键数：
  7
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.22
• 拓扑面积：
  43.4
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为产物：
  描述：

  methyl (R)-5-(((S)-3-(methoxymethyl)-3,4-dihydroisoquinolin-2(1H)-yl)imino)-3,5-diphenylpentanoate 在 碘甲烷 、 盐酸 、 水 作用下， 以 正戊烷 为溶剂， 反应 48.5h， 以91%的产率得到(R)-methyl-5-oxo-3,5-diphenylpentanoate
  参考文献：
  名称：

  The preparation of novel chiral auxiliaries SAMIQ/RAMIQ and their application in the asymmetric Michael addition

  摘要：

  A pair of novel chiral auxiliaries SAMIQ/RAMIQ was synthesized from L- or D-phenylalanine methyl ester hydrochloride over six steps in 45.8% and 44.4% yield, respectively. The SAMIQ-/RAMIQ-hydrazone methodology was applied for the asymmetric Michael addition of ketones to alpha,beta-unsaturated carboxylic acid methyl esters, which afforded 3-substituted-5-oxo-alkanoates in moderate to good yield (65-82%) with excellent enantioselectivity (ee=95.3%similar to>99.5%). (C) 2014 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tet.2014.05.049

文献信息

• Enantioselective Mukaiyama-Michael Reaction Catalyzed by a Chiral Rhodium Complex Based on Pinene-Modified Pyridine Ligands
  作者：Jun Gong、Qian Wan、Qiang Kang

  DOI：10.1002/asia.201800318

  日期：2018.9.4

  rhodium complex Λ‐Rh1 containing chiral pinene‐modified pyridine ligands is prepared through a two‐step synthetic procedure; it exhibits excellent reactivity and enantiocontrol towards the enantioselective Mukaiyama–Michael reaction of α,β‐unsaturated 2‐acyl imidazoles with silyl enol ethers, affording enantioenriched 1,5‐dicarbonyl compounds in good yields (up to 99 %) with excellent enantioselectivities

  含有手性complex烯修饰的吡啶配体的铑配合物 Λ-Rh1是通过两步合成程序制备的；它对α，β-不饱和2-酰基咪唑与甲硅烷基烯醇醚的对映选择性Mukaiyama-Michael反应表现出优异的反应性和对映体控制性能，可提供高收率（高达99％）的对映体富集的1,5-二羰基化合物，并具有出色的对映选择性（高达到99％ee）。
• Enantioselective Mukaiyama-Michael Reaction of Silyl Enol Ethers to 2-Enoylpyridine<i>N</i>-Oxides Catalyzed by Copper- Bis(oxazoline) Complex
  作者：Jimil George、Basi V. Subba Reddy

  DOI：10.1002/adsc.201200631

  日期：2013.1.16

  A catalytic enantioselective Mukaiyama–Michael reaction of 2-enoylpyridine N-oxides has been developed using a simple bis(oxazoline)-copper complex. A variety of silyl enol ethers undergo smooth Michael addition with 2-enoylpyridine N-oxides to furnish the corresponding Michael adducts in high yields with high enantioselectivities (up to 97% ee).

  使用简单的双（恶唑啉）-铜配合物开发了2-烯丙基吡啶N-氧化物的催化对映选择性Mukaiyama-Michael反应。各种甲硅烷基烯醇醚与2-烯丙基吡啶N-氧化物进行平滑的迈克尔加成反应，以高收率和高对映选择性（高达97％ee）提供相应的迈克尔加合物。
• 手性金属铑配合物、其合成方法、及其在合成手性1,5-二羰基化合物中的应用
  申请人：中国科学院福建物质结构研究所

  公开号：CN110041371A

  公开（公告）日：2019-07-23

  本发明公开了一种手性金属铑配合物、其合成方法、及其在合成手性1,5‑二羰基化合物中的应用，其中手性金属铑配合物合成方法包括以下步骤：a)RhX3与L‑手性蒎烯吡啶进行第一反应得到手性Rh‑X；b)手性Rh‑X与烷基腈化合物进行第二反应制得手性金属铑配合物。该方法简单易操作，可用于催化多种不同类型的α,β‑不饱和酰基咪唑和烯醇硅醚类化合物。
• Enantioselective [3 + 3] Annulation–Deoxalation Strategy for Rapid Access to δ-Oxoesters via N-Heterocyclic Carbene Catalysis
  作者：Izabela Barańska、Liliana Dobrzańska、Zbigniew Rafiński

  DOI：10.1021/acs.orglett.3c04397

  日期：2024.2.16

  unprecedented stereoselective synthetic approach to δ-oxoesters derivatives from readily available starting materials has been developed. This method, catalyzed by N-heterocyclic carbene, involves an annulation–deoxalation reaction of alkynyl aldehydes with 2,4-diketoesters and proceeds via the chiral α,β-unsaturated acylazolium intermediates. The annulation includes the in situ formation of dihydropyranones

  开发了一种新的、前所未有的立体选择性合成方法，从容易获得的起始材料中合成 δ-氧代酯衍生物。该方法由 N-杂环卡宾催化，涉及炔醛与 2,4-二酮酯的环化-脱草反应，并通过手性 α,β-不饱和酰唑鎓中间体进行。成环包括原位形成二氢吡喃酮，二氢吡喃酮在路易斯酸活化下进行开环甲醇分解，然后进行脱草作用，以中等至良好的收率得到手性 1,5-酮酯。
• Ligand differentiated complementary Rh-catalyst systems for the enantioselective desymmetrization of meso-cyclic anhydrides
  作者：Jeffrey B. Johnson、Matthew J. Cook、Tomislav Rovis

  DOI：10.1016/j.tet.2008.10.075

  日期：2009.4

  Two distinct systems for the rhodium-catalyzed enantioselective desymmetrization of meso-cyclic anhydrides have been developed. Each system has been optimized and are compatible with the use of in situ prepared organozinc reagents. Rhodium/PHOX species efficiently catalyze the addition of alkyi nucleophiles to glutaric anhydrides, while system is effective in the enantioselective arylation of succinic and glutaric anhydrides. (C) 2008 Elsevier Ltd. All rights reserved.