(R)-2-oxo-2,4-diphenylbutanal

• 分子结构分类: 有机化合物 - 苯丙烷和聚酮 - 直链 1,3-二芳基丙烷
• 英文名称: (R)-2-oxo-2,4-diphenylbutanal
• 英文别名: (2R)-4-oxo-2,4-diphenylbutanal
• 化学式: C₁₆H₁₄O₂
• 分子量: 238.286
• InChiKey: ANXWUEKPYVKZCJ-HNNXBMFYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.7
• 重原子数：
  18
• 可旋转键数：
  5
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.12
• 拓扑面积：
  34.1
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为产物：
  描述：

  (1R,3R)-2-phenylmethylidene-1λ⁴,3λ⁴-dithiane-1,3-dioxide 在 [ReOCl₃(PPh₃)₂] 、 sodium hexamethyldisilazane 、 三苯基膦 、 [双(三氟乙酰氧基)碘]苯 作用下， 以 四氢呋喃 、 二氯甲烷 、 水 、 乙腈 为溶剂， 反应 12.92h， 生成 (R)-2-oxo-2,4-diphenylbutanal
  参考文献：
  名称：

  Enolate Addition to a 2-Alkylidene[1,3]dithiane-Derived Bissulfoxide. A New a²-Acceptor

  摘要：

  Reaction of enolates derived from esters and ketones to an easily prepared alkylidene[1,3]dithiane-1,3-dioxide afforded the respective adducts with good yields and selectivities generally exceeding 85:15. The base used for enolate addition played no significant role for the reaction outcome, and addition of a silyl enole ether gave similar results. The thus formed oxygenated S,S-acetals were transformed into the corresponding 1,4-dicarbonyls by a reduction/oxidation sequence with 84% yield.

  DOI：

  10.1021/ol051670i

文献信息

• Palladium-Catalyzed Diastereoselective and Enantioselective Allylic Alkylations of Ketone Enolates
  作者：Manfred Braun、Thorsten Meier、Frank Laicher、Panos Meletis、Mesut Fidan

  DOI：10.1002/adsc.200700409

  日期：2008.1.25

  the lithium enolates, the presence of lithium chloride is also crucial to reactivity and stereoselectivity. The stereochemical outcome of the allylic alkylation of cyclohexanone and acetophenone has been investigated by the palladium-catalyzed reaction of their lithium enolates with the cis/trans isomeric alkenes (Z)-18 and (E)-19. It turns out that the preformed, non-stabilized enolates attack π-allyl-palladium

  环己酮的锂和镁的烯醇化物在温和的条件下经历钯催化的烯丙基烷基化反应。当二苯基和二甲基取代的烯丙基底物1a和1b与环己酮或乙基异丁基酮反应时，观察到非对映选择性和对映选择性。环己酮，环戊酮和α-四氢萘酮的烯醇锂导致烷基化产物12 – 14以对映选择性的方式。轴向手性联苯基和联萘基双膦提供高对映选择性和/或非对映选择性。就烯醇锂而言，氯化锂的存在对反应性和立体选择性也至关重要。环己酮和苯乙酮的烯丙基烷基化的立体化学结果已通过钯催化的其烯醇锂与顺式/反式异构烯烃（Z）-18和（E）-19的反应进行了研究。事实证明，预先形成的不稳定的烯醇盐会攻击原位生成的π-烯丙基-钯配合物 从与贵金属相反的表面开始，因此遵循了柔软，稳定的碳负离子的立体化学路径。
• Palladium-Catalyzed Stereoselective Allylic Alkylation of Lithium Enolates
  作者：Manfred Braun、Thorsten Meier

  DOI：10.1055/s-2005-921908

  日期：——

  The lithium enolates, generated from cyclohexanone, cyclopentanone, and 1-tetralone, react with allyl acetate 1b or carbonate Ic enantioselectively, when catalyzed by (R)- or (S)-BINAP-derived palladium complexes. The presence of lithium chloride is crucial to stereoselectivity. Diastereoselective and enantioselective allylation occurs between cyclohexanone and carbonate 1d. It is shown in the case

  当由 (R)- 或 (S)-BINAP 衍生的钯配合物催化时，由环己酮、环戊酮和 1-四氢萘酮生成的锂烯醇化物与乙酸烯丙酯 1b 或碳酸酯 Ic 对映选择性反应。氯化锂的存在对立体选择性至关重要。非对映选择性和对映选择性烯丙基化发生在环己酮和碳酸酯 1d 之间。在无环底物 (Z)-12 和 (E)-17 的情况下表明，n-烯丙基钯配合物从与贵金属相反的面受到锂烯醇化物的攻击。
• Enantioselective Nucleophilic Formylation and Cyanation of Conjugated Enones <i>via</i> Michael Addition of Formaldehyde SAMP-Hydrazone
  作者：Jose-María Lassaletta、Rosario Fernández、Eloísa Martín-Zamora、Elena Díez

  DOI：10.1021/ja9610500

  日期：1996.1.1
• Formaldehyde Dialkylhydrazones as Neutral Formyl Anion and Cyanide Equivalents:  Nucleophilic Addition to Conjugated Enones
  作者：Elena Díez、Rosario Fernández、Consolación Gasch、José M. Lassaletta、José M. Llera、Eloísa Martín-Zamora、Juan Vázquez

  DOI：10.1021/jo970481d

  日期：1997.7.1

  A versatile methodology for the nucleophilic formylation and cyanation of conjugated enones is reported. The procedure is based on the use of formaldehyde dimethylhydrazone, which, acting as a neutral formyl anion equivalent, adds to preformed trialkylsilyl-enone complexes. Both 4-(silyloxy)-3-enal hydrazones 3 or deprotected 4-oxo aldehyde monohydrazones 4 can be obtained as products depending on quenching conditions. In full analogy, an asymmetric version of the reaction using chiral formaldehyde SAMP-hydrazone as a neutral synthon of the chiral formyl anion has been developed, giving rise to the corresponding adducts 5 and 6 in good yields and with excellent diastereoselectivities (de 85-greater than or equal to 98%). Ozonolysis or HCl-mediated hydrolysis of adducts 4 and 6 readily affords racemic and optically enriched 4-oxo aldehydes 7, respectively. Additionally, high-yielding MMPP-oxidative cleavage of 4-oxo hydrazones 4 and 6 has been performed to obtain Li-oxo nitriles 8 in racemic and optically enriched forms, respectively. In this way, interesting chiral bifunctional building blocks, some of them bearing newly created stereogenic quaternary centers, have been efficiently synthesized.
• Enolate Addition to a 2-Alkylidene[1,3]dithiane-Derived Bissulfoxide. A New a²-Acceptor
  作者：Tobias Wedel、Joachim Podlech

  DOI：10.1021/ol051670i

  日期：2005.9.1

  Reaction of enolates derived from esters and ketones to an easily prepared alkylidene[1,3]dithiane-1,3-dioxide afforded the respective adducts with good yields and selectivities generally exceeding 85:15. The base used for enolate addition played no significant role for the reaction outcome, and addition of a silyl enole ether gave similar results. The thus formed oxygenated S,S-acetals were transformed into the corresponding 1,4-dicarbonyls by a reduction/oxidation sequence with 84% yield.