(E)-diisopropyl cinnamoylphosphonate

• 分子结构分类: 有机化合物 - 苯丙烷和聚酮 - 肉桂酸及其衍生物
• 英文名称: (E)-diisopropyl cinnamoylphosphonate
• 英文别名: (E)-1-di(propan-2-yloxy)phosphoryl-3-phenylprop-2-en-1-one
• 化学式: C₁₅H₂₁O₄P
• 分子量: 296.303
• InChiKey: CCLDIHYHNLDJQC-ZHACJKMWSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.9
• 重原子数：
  20
• 可旋转键数：
  7
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.4
• 拓扑面积：
  52.6
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  (E)-diisopropyl cinnamoylphosphonate 在 三甲基乙酰氯 、 二异丁基氢化铝 、 N,N-二异丙基乙胺 作用下， 以 四氢呋喃 、 二氯甲烷 、 甲苯 为溶剂， 反应 49.83h， 生成 methyl (2R,3R)-5-hydroxy-2,3-diphenylpentanoate
  参考文献：
  名称：

  α-Ketophosphonates as Ester Surrogates: Isothiourea-Catalyzed Asymmetric Diester and Lactone Synthesis

  摘要：

  Isothiourea HBTM-2.1 catalyzes the asymmetric Michael addition/lactonization of aryl- and alkenylacetic acids using alpha-keto-beta,gamma-unsaturated phosphonates as alpha,beta-unsaturated ester surrogates, giving access to a diverse range of stereodefined lactones or enantioenriched functionalized diesters upon ring-opening.

  DOI：

  10.1021/ol500873s
• 作为产物：
  描述：

  (E)-diisopropyl (1-hydroxy-3-phenylallyl)phosphonate 在 三氧化硫吡啶 、 N,N-二异丙基乙胺 作用下， 以 二氯甲烷 、 二甲基亚砜 为溶剂， 反应 1.0h， 以2.41 g的产率得到(E)-diisopropyl cinnamoylphosphonate
  参考文献：
  名称：

  烷基芳基烯酮与 β,γ-不饱和 α-酮膦酸酯的对映选择性 NHC 催化的 [4+2] 环加成反应

  摘要：

  描述了 NHC 介导的对映选择性形式 [4+2] 烷芳基烯酮与 γ-取代-β,γ-不饱和 α-酮膦酸酯的环加成反应。观察到非对映选择性的底物依赖性转换，γ-芳基α-酮膦酸酯优先提供顺式二氢吡喃酮膦酸酯和γ-甲基α-酮膦酸酯，有利于抗二氢吡喃酮膦酸酯。此外，与相应的两步法相比，原位生成乙烯酮保留了高水平的立体选择性并提高了产品收率。

  DOI：

  10.1055/s-0033-1338851

文献信息

• Organocatalytic Access to Enantioenriched Dihydropyran Phosphonates via an Inverse-Electron-Demand Hetero-Diels–Alder Reaction
  作者：Christian F. Weise、Vibeke H. Lauridsen、Raoní S. Rambo、Eva H. Iversen、Marie-Luise Olsen、Karl Anker Jørgensen

  DOI：10.1021/jo500347a

  日期：2014.4.18

  hetero-Diels–Alder reaction of the remote olefin functionality in dienamines has been developed by the simultaneous activation of α,β-unsaturated aldehydes and acyl phosphonates. The dual activation is based on an organocatalyst that activates both the α,β-unsaturated aldehyde, through dienamine formation, and the acyl phosphonate by hydrogen-bonding. The enantioselective reaction results in the formation

  通过同时激活α，β-不饱和醛和酰基膦酸酯，开发了二烯胺中远程烯烃官能团的对映选择性逆电子需杂Diels-Alder反应。双重活化基于有机催化剂，该有机催化剂通过二烯胺的形成来活化α，β-不饱和醛，并通过氢键来活化酰基膦酸酯。对映选择性反应导致形成具有三个连续的立体中心的二氢吡喃骨架。杂二烯和亲二烯体都可能有不同的取代方式，并且目标产物以良好的收率和高达92％的ee获得。通过将产物转化为有价值的和复杂的合成子来证明反应的潜力。
• Asymmetric synthesis of Rauhut–Currier-type esters <i>via</i> Mukaiyama–Michael reaction to acylphosphonates under bifunctional catalysis
  作者：Víctor Laina-Martín、Roberto del Río-Rodríguez、Sergio Díaz-Tendero、Jose A. Fernández-Salas、José Alemán

  DOI：10.1039/c8cc07561a

  日期：——

  A highly enantioselective organocatalytic Mukaiyama–Michael reaction of silyloxy dienes and α,β-unsaturated acyl phosphonates under bifunctional organocatalysis is presented. The new reactivity triggered by the catalyst conducted to Rauhut–Currier type esters, via a formal conjugate addition to α,β-unsaturated esters. This protocol proceeds under mild conditions with complete regioselectivity and excellent

  介绍了在双功能有机催化下甲硅烷氧基二烯和 α,β-不饱和酰基膦酸酯的高度对映选择性有机催化 Mukaiyama-Michael 反应。新的反应性通过传导到劳胡特-柯里尔型酯催化剂触发，经由一个正式的共轭加成到α，β不饱和酯。该协议在温和的条件下进行，具有完全的区域选择性和出色的对映控制。
• Enantioselective NHC-Catalysed Formal [4+2] Cycloaddition of Alkylaryl­ketenes with β,γ-Unsaturated α-Ketophosphonates
  作者：Andrew Smith、Stuart Leckie、Charlene Fallan、James Taylor、T. Brown、David Pryde、Tomáš Lébl、Alexandra Slawin

  DOI：10.1055/s-0033-1338851

  日期：——

  NHC-mediated enantioselective formal [4+2] cycloadditions of alkylarylketenes with γ-substituted-β,γ-unsaturated α-ketophosphonates is described. A substrate-dependent switch in diastereoselectivity was observed, with γ-aryl α-ketophosphonates providing preferentially the syn-dihydropyranone-phosphonates and γ-methyl α-ketophosphonates favouring the anti-dihydropyranone-phosphonate. In addition, ketene generation

  描述了 NHC 介导的对映选择性形式 [4+2] 烷芳基烯酮与 γ-取代-β,γ-不饱和 α-酮膦酸酯的环加成反应。观察到非对映选择性的底物依赖性转换，γ-芳基α-酮膦酸酯优先提供顺式二氢吡喃酮膦酸酯和γ-甲基α-酮膦酸酯，有利于抗二氢吡喃酮膦酸酯。此外，与相应的两步法相比，原位生成乙烯酮保留了高水平的立体选择性并提高了产品收率。
• DABCO-catalyzed regioselective cyclization reactions of β,γ-unsaturated α-ketophosphonates or β,γ-unsaturated α-ketoesters with allenic esters
  作者：Cheng-Kui Pei、Lei Wu、Zhong Lian、Min Shi

  DOI：10.1039/c1ob06507f

  日期：——

  Highly efficient DABCO-catalyzed [4 + 2] cycloaddition of β,γ-unsaturated α-ketophosphonates or β,γ-unsaturated α-ketoesters with allenic esters gives the corresponding highly functionalized tetrahydropyran and dihydropyran derivatives in good to excellent yields and moderate to good regioselectivities under mild conditions.

  高效的DABCO催化的[4 + 2]与烯丙酸酯的β，γ-不饱和α-酮膦酸酯或β，γ-不饱和α-酮酸酯的环加成反应得到相应的高度官能化 四氢吡喃 和二氢吡喃衍生物，在温和条件下具有良好至优异的收率和中等至良好的区域选择性。
• Enantioselective Synthesis of Highly Functionalized Phosphonate-Substituted Pyrans or Dihydropyrans Through Asymmetric [4+2] Cycloaddition of β,γ-Unsaturated α-Ketophosphonates with Allenic Esters
  作者：Cheng-Kui Pei、Yu Jiang、Yin Wei、Min Shi

  DOI：10.1002/anie.201206958

  日期：2012.11.5

  Tell me which you want: Catalytic asymmetric [4+2] cycloadditions of β,γ‐unsaturated α‐ketophosphonates with allenic esters catalyzed by organocatalysts derived from different cinchona alkaloids have been developed, affording phosphonate‐substituted functionalized pyran and dihydropyran derivatives in excellent yields with high enantioselectivities under mild conditions. The choice of product is controlled

  告诉我你想要什么：已经开发了由不同金鸡纳生物碱衍生的有机催化剂催化的不对称[4 + 2]β，γ-不饱和α-酮膦酸酯与烯丙基酯的环加成反应，从而以优异的产率提供了膦酸酯取代的官能化吡喃和二氢吡喃衍生物。在温和条件下具有高对映选择性。产物的选择由所选催化剂的氢键特征控制。