trans-4,5-diphenyldihydrofuran-2(3H)-one

• 分子结构分类: 有机化合物 - 苯丙烷和聚酮 - 二苯乙烯类
• 英文名称: trans-4,5-diphenyldihydrofuran-2(3H)-one
• 英文别名: (4R,5S)-4,5-diphenyloxolan-2-one
• 化学式: C₁₆H₁₄O₂
• 分子量: 238.286
• InChiKey: HSIFUOWGIIPHFW-GDBMZVCRSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.1
• 重原子数：
  18
• 可旋转键数：
  2
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.19
• 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：

  trans-4,5-diphenyldihydrofuran-2(3H)-one 在 dimethyl sulfide borane 、 水 、 三乙胺 、 甘油 作用下， 以 二氯甲烷 为溶剂， 生成 Methanesulfonic acid (1S,2R)-4-methanesulfonyloxy-1,2-diphenyl-butyl ester
  参考文献：
  名称：

  Regio-, stereo-, and enantioselectivity in the electrophilic reactions of 2-amino-4-phenyl-3-butenenitriles

  摘要：

  The allylic anion generated from 2-(N-methylanilino)-4-phenyl-3-butenenitrile (1) reacted with iodomethane and 3-bromo-1-chloropropane in THF/HMPA to give the gamma-substitution products exclusively, predominantly in the 2Z-configuration. Substitution of the N-methylanilino group with the methyl ether of L-(-)-ephedrine resulted in the generation of chiral aminonitrile 2. Lithiated 2 reacted sluggishly in THF with allyl bromide and benzyl chloride in the absence of HMPA to give the gamma-substitution products predominantly in the 2Z-configuration, with little diastereoselectivity. The aminonitrile 3 prepared from cinnamaldehyde, L-(-)-ephedrine, and KCN was lithiated with 2 equiv of LDA resulting in high facial selectivity (76-100% diastereomeric excess) in alkylations in the presence of HMPA and LiI. Lithiated 3 reacted with propionaldehyde, benzaldehyde, and p-bromobenzaldehyde at-78-degrees-C to give the gamma-addition products, predominantly in the 4R-configuration (64-78% de). The stereochemistry of the isomers of each product was determined by chemical correlation and spectral methods including analyses of the CD spectra and X-ray diffraction. A bicyclic transition state C wherein lithium is chelated by both amino and alkoxy groups is proposed to interpret the observed stereoselectivity.

  DOI：

  10.1021/jo00059a027
• 作为产物：
  描述：

  N,N-二甲基-2-苯基乙酰胺 在 2,4,6-三甲基吡啶 、 三氟甲磺酸酐 、 间氯过氧苯甲酸 作用下， 以 二氯甲烷 、 氯仿 为溶剂， 反应 16.0h， 生成 trans-4,5-diphenyldihydrofuran-2(3H)-one
  参考文献：
  名称：

  单个C–C键的多个铑催化裂解

  摘要：

  Rh（I）催化的顺式和反式不对称取代的亚烷基环丁烷的分子内氢酰化反应根据三种机理途径进行。如氘标记实验所示，解释顺式异构体重排的机理包括三个碳-碳键的断裂和显着的跨环3-exo-trig碳金属化。

  DOI：

  10.1021/ol400266g

文献信息

• Silyl Phosphites. XVIII. Versatile Utility of α-(Trimethylsilyloxy)alkylphosphonates as Key Intermediates for Transformation of Aldehydes into Several Carbonyl Derivatives
  作者：Mitsuo Sekine、Masashi Nakajima、Akiko Kume、Akio Hashizume、Tsujiaki Hata

  DOI：10.1246/bcsj.55.224

  日期：1982.1

  trimethylsilyl phosphite (DTMSP) with aldehydes were converted, by treatment with lithium diisopropylamide (LDA) followed by the successive alkylation and alkaline hydrolysis, to carbonyl derivatives involving aldehydes, unsymmetrical ketones, β,γ-unsaturated ketones, and carboxylic acids. β-Substituted carboxylic esters and γ-substituted lactones were prepared by use of the carbonyl addition compounds of DTMSP

  通过用二异丙基氨基锂 (LDA) 处理，然后连续烷基化和碱水解，将二乙基三甲基甲硅烷基亚磷酸酯 (DTMSP) 与醛的羰基加成化合物转化为涉及醛、不对称酮、β,γ-不饱和酮和羧酸的羰基衍生物酸。利用DTMSP的羰基加成化合物与α,β-不饱和醛制备β-取代羧酸酯和γ-取代内酯。
• MnO₂-promoted carboesterification of alkenes with anhydrides: a facile approach to γ-lactones
  作者：Lihuan Wu、Zhenming Zhang、Jianhua Liao、Jianxiao Li、Wanqing Wu、Huanfeng Jiang

  DOI：10.1039/c5cc08867d

  日期：——

  A new radical cyclization method for the formation of C(sp³)–C(sp³) and C–O bonds via MnO₂-promoted alkene carboesterification with anhydrides is developed.

  一种新的基于锰促进的烯烃碳酯化反应的C(sp3)-C(sp3)和C-O键的放射状环化方法被开发出来。
• Mechanisms for Manganese(III) Oxidations with Alkenes
  作者：William E. Fristad、John R. Peterson、Andreas B. Ernst、Gordon B. Urbi

  DOI：10.1016/s0040-4020(01)87310-5

  日期：1986.1

  metal complexed organic radicals, and the importance of an oxo-centered manganese(III) triangle are discussed as they relate to the lactone annulation reaction. Single electron transfer oxidation of alkenes is described as a route toward 1,2-diacetates of alkenes within the 8.1-7.5 eV I.P. range. Three less common modes of Mn(III) reaction are discussed and compared with the two primary processes of

  在乙酸锰（III）与羧酸和烯烃的反应中，已经鉴定出三个不同的过程，它们涉及烯烃和两个独立于烯烃的过程。通过产品研究，重排，稀释实验和文献动力学数据的组合，可以提出一个统一的机制图来描述这些过程。具体地，讨论了羧酸组分的α-H酸的作用，缺电子的自由基加成，金属络合的有机自由基以及以氧代为中心的锰（III）三角形的重要性，因为它们与内酯环化反应有关。烯烃的单电子转移氧化被描述为通往8.1-7.5 eV IP范围内的烯烃1,2-二乙酸酯的途径。
• Visible-Light Photoredox-Catalyzed Hydroalkoxymethylation of Activated Alkenes Using α-Silyl Ethers as Alkoxymethyl Radical Equivalents
  作者：Nilufa Khatun、Myeong Jun Kim、Sang Kook Woo

  DOI：10.1021/acs.orglett.8b02721

  日期：2018.10.5

  electron oxidation (SET) of α-TMS-substituted ethers, followed by subsequent conjugate addition to activated alkenes. Various functional groups were tolerated both under mild metal and metal-free conditions to provide good to excellent yields. Furthermore, the addition products were transformed to valuable synthetic building blocks, such as carboxylic acids, γ-butyrolactones, and complex aryl alkyl ethers

  提出了一种新型的基于中性硅的无痕活化基团（TAG），用于可见光的光氧化还原催化的烯烃的加氢烷氧基甲基化。该反应涉及通过α-TMS-取代的醚的单电子氧化（SET）原位产生的烷氧基甲基自由基，随后将共轭物加成至活化的烯烃中。在温和的金属和不含金属的条件下都可以耐受各种官能团，从而提供了良好的优异收率。此外，将加成产物转化为有价值的合成构件，例如羧酸，γ-丁内酯和复杂的芳基烷基醚。
• Mn(OAc)₃-mediated arylation–lactonization of alkenoic acids: synthesis of γ,γ-disubstituted butyrolactones
  作者：Yuzhen Gao、Jian Xu、Pengbo Zhang、Hua Fang、Guo Tang、Yufen Zhao

  DOI：10.1039/c5ra04429d

  日期：——

  A general method for the synthesis of γ,γ-disubstituted butyrolactones via an arylation–lactonization of alkenoic acids process has been developed.

  通过芳基化-内酯化烯酸的方法，已经开发出一种合成γ,γ-二取代丁内酯的一般方法。