2-diethylphosphoryloxy-2-(3,5-dimethoxyphenyl)-1-phenylethanone

• 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: 2-diethylphosphoryloxy-2-(3,5-dimethoxyphenyl)-1-phenylethanone
• 英文别名: diethyl 1-(3,5-dimethoxyphenyl)-2-oxo-2-phenylethyl phosphate；Diethyl 3',5'-dimethoxybenzoinyl phosphate；3',5'-dimethoxybenzoin diethyl phosphate；DMB diethyl phosphate；[1-(3,5-Dimethoxyphenyl)-2-oxo-2-phenylethyl] diethyl phosphate
• 化学式: C₂₀H₂₅O₇P
• 分子量: 408.388
• InChiKey: DPTZJQWRWZLACG-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.3
• 重原子数：
  28
• 可旋转键数：
  11
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.35
• 拓扑面积：
  80.3
• 氢给体数：
  0
• 氢受体数：
  7

反应信息

• 作为反应物：
  描述：

  2-diethylphosphoryloxy-2-(3,5-dimethoxyphenyl)-1-phenylethanone 以 乙腈 为溶剂， 生成 4,6-dimethoxy-2-phenylbenzofuran
  参考文献：
  名称：

  双发色光触发物3'，5'-二甲氧基安息香磷酸二乙酯的时间分辨光谱研究：两个发色团之间的相互作用决定了反应途径

  摘要：

  3'，5'-二甲氧基安息香（DMB）是一种双发色体系，已广泛用作释放各种官能团的高效光可移除保护基（PRPG）。DMB光触发的光脱保护非常干净，并伴随着生物良性环化产物3'，5'-二甲氧基苯并呋喃（DMBF）的形成。但是，直到现在，DMB脱保护和环化的基本机制仍不清楚。飞秒瞬态吸收（fs‐TA）光谱和纳秒时间分辨共振拉曼（ns‐TR 3）光谱可直接检测瞬态物质，并检查DMB磷酸二乙酯（DMBDP）初级光反应中涉及的动态转变。乙腈（CH 3CN）。为了评估电子特性，并通过各个子类生色团发挥的作用，也就是苯甲酰和二元为了使DMBDP脱保护，在相同溶剂中还对参考化合物磷酸二乙酯苯乙酮（DPAP）和3'，5'-二甲氧基苄基二乙基磷酸酯（DMBnDP）进行了fs-TA对比-甲氧基苄基部分。fs-TA光谱的比较表明，光激发的DMBDP与参考化合物相比具有明显不同的光谱特性和动态演化。这一事实与相关的稳

  DOI：

  10.1002/chem.200902891
• 作为产物：
  描述：

  α-(3,5-dimethoxyphenyl)-α-(trimethylsilyloxy)acetonitrile 在 盐酸 、 水 、 碘 、 N,N-二异丙基乙胺 作用下， 反应 7.25h， 生成 2-diethylphosphoryloxy-2-(3,5-dimethoxyphenyl)-1-phenylethanone
  参考文献：
  名称：

  Photoremovable Protecting Groups for Phosphorylation of Chiral Alcohols. Asymmetric Synthesis of Phosphotriesters of (-)-3',5'-Dimethoxybenzoin

  摘要：

  Procedures have been developed for the preparation of dimethoxybenzoinyl (DMB) phosphate triesters that can be deprotected photochemically. These compounds can be useful in light-directed synthesis and caging. The photochemistry of a wide variety of fluorine-, oxygen-, and nitrogen-substituted benzoin acetates was examined to determine the substitution pattern in the nonacylated aromatic ring producing optimum chemical yields. Two groups, 2',3'-dimethoxybenzoin and 3',5'dimethoxybenzoin, were found to give the highest yields of the benzofuran product and were further developed for the photochemical deprotection of phosphate esters. These reactions could not be quenched, suggesting a singlet photosolvolysis mechanism. An asymmetric synthesis of 3',5'dimethoxybenzoin via the benzaldehyde cyanohydrin was developed that minimizes the number of diastereomers formed in the phosphorylation of chiral alcohols. A phosphoramidite reagent for the derivatization of alcohols was prepared and used to produce scalemic dimethoxybenzoinyl phosphate esters from pantolactone and glycerol, serine, and tyrosine derivatives. These compounds were deprotected photochemically to produce the phosphodiesters in high yield.

  DOI：

  10.1021/jo00093a021

文献信息

• Cyanide-Catalyzed Additions of Acyl Phosphonates to Aldehydes: A New Acyl Donor for Benzoin-Type Reactions
  作者：Cory C. Bausch、Jeffrey S. Johnson

  DOI：10.1002/adsc.200505097

  日期：2005.7

  phosphonates, followed by a [1,2]-phosphoryl migration generates the active acyl anion intermediate. The presumed (cyano)phosphate anion reacts with a variety of aryl aldehydes to yield phosphate ester-protected, unsymmetrical benzoins in good to excellent yields. The unsymmetrical benzoin product can be obtained after deprotection of the phosphate ester with an aqueous amine solution.

  酰基膦酸酯已被用作氰化物催化的安息香型反应的新的酰基供体。酰基膦酸酯的氰化，然后是[1,2]-磷酰基迁移，生成了活性的酰基阴离子中间体。推测的（氰基）磷酸根阴离子与各种芳基醛反应，生成磷酸酯保护的不对称安息香，收率良好至极佳。在用胺水溶液使磷酸酯脱保护后，可以获得不对称的安息香产物。
• Generation of Acyl Anion Equivalents from Acylphosphonates via Phosphonate−Phosphate Rearrangement:  A Highly Practical Method for Cross-Benzoin Reaction
  作者：Ayhan S. Demir、Ömer Reis、A. Çiǧdem İǧdir、İlker Esiringü、Serkan Eymur

  DOI：10.1021/jo051811u

  日期：2005.12.1

  Acylphosphonates are potent acyl anion precursors that generate acyl anion equivalents under the promotion of cyanide anion via phosphonate−phosphate rearrangement. These anions readily react with aldehydes to provide cross-benzoin products. In this way it is possible to synthesize a variety of aromatic−aromatic, aromatic−aliphatic, and aliphatic−aromatic benzoins. Moreover the reaction of benzoylphosphonate

  酰基膦酸酯是有效的酰基阴离子前体，可通过膦酸酯-磷酸重排在氰化物阴离子的促进下生成酰基阴离子当量。这些阴离子容易与醛反应以提供交叉安息香产物。通过这种方式，可以合成各种芳族-芳族，芳族-脂族和脂族-芳族苯偶姻。此外，苯甲酰基膦酸酯与强力亲电子试剂2,2,2-三氟苯乙酮的反应以高收率提供了相应的醛-酮偶联产物。
• Photoremovable Protecting Groups for Phosphorylation of Chiral Alcohols. Asymmetric Synthesis of Phosphotriesters of (-)-3',5'-Dimethoxybenzoin
  作者：Michael C. Pirrung、Steven W. Shuey

  DOI：10.1021/jo00093a021

  日期：1994.7

  Procedures have been developed for the preparation of dimethoxybenzoinyl (DMB) phosphate triesters that can be deprotected photochemically. These compounds can be useful in light-directed synthesis and caging. The photochemistry of a wide variety of fluorine-, oxygen-, and nitrogen-substituted benzoin acetates was examined to determine the substitution pattern in the nonacylated aromatic ring producing optimum chemical yields. Two groups, 2',3'-dimethoxybenzoin and 3',5'dimethoxybenzoin, were found to give the highest yields of the benzofuran product and were further developed for the photochemical deprotection of phosphate esters. These reactions could not be quenched, suggesting a singlet photosolvolysis mechanism. An asymmetric synthesis of 3',5'dimethoxybenzoin via the benzaldehyde cyanohydrin was developed that minimizes the number of diastereomers formed in the phosphorylation of chiral alcohols. A phosphoramidite reagent for the derivatization of alcohols was prepared and used to produce scalemic dimethoxybenzoinyl phosphate esters from pantolactone and glycerol, serine, and tyrosine derivatives. These compounds were deprotected photochemically to produce the phosphodiesters in high yield.
• A Time-Resolved Spectroscopic Study of the Bichromophoric Phototrigger 3′,5′-Dimethoxybenzoin Diethyl Phosphate: Interaction Between the Two Chromophores Determines the Reaction Pathway
  作者：Chensheng Ma、Wai Ming Kwok、Hui-Ying An、Xiangguo Guan、Michael Yunyi Fu、Patrick H. Toy、David Lee Phillips

  DOI：10.1002/chem.200902891

  日期：——

  5′‐dimethoxybenzofuran (DMBF). The underlying mechanism of the DMB deprotection and cyclization has, however, until now remained unclear. Femtosecond transient absorption (fs‐TA) spectroscopy and nanosecond time‐resolved resonance Raman (ns‐TR3) spectroscopy were employed to detect the transient species directly, and examine the dynamic transformations involved in the primary photoreactions for DMB diethyl phosphate

  3'，5'-二甲氧基安息香（DMB）是一种双发色体系，已广泛用作释放各种官能团的高效光可移除保护基（PRPG）。DMB光触发的光脱保护非常干净，并伴随着生物良性环化产物3'，5'-二甲氧基苯并呋喃（DMBF）的形成。但是，直到现在，DMB脱保护和环化的基本机制仍不清楚。飞秒瞬态吸收（fs‐TA）光谱和纳秒时间分辨共振拉曼（ns‐TR 3）光谱可直接检测瞬态物质，并检查DMB磷酸二乙酯（DMBDP）初级光反应中涉及的动态转变。乙腈（CH 3CN）。为了评估电子特性，并通过各个子类生色团发挥的作用，也就是苯甲酰和二元为了使DMBDP脱保护，在相同溶剂中还对参考化合物磷酸二乙酯苯乙酮（DPAP）和3'，5'-二甲氧基苄基二乙基磷酸酯（DMBnDP）进行了fs-TA对比-甲氧基苄基部分。fs-TA光谱的比较表明，光激发的DMBDP与参考化合物相比具有明显不同的光谱特性和动态演化。这一事实与相关的稳