(3,6-dimethoxy-2-iodophenyl)diphenylphosphine oxide | 136202-05-6

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: (3,6-dimethoxy-2-iodophenyl)diphenylphosphine oxide
• 英文别名: (2,5-dimethoxyphenyl)diphenylphosphine oxide；2-Diphenylphosphoryl-3-iodo-1,4-dimethoxybenzene
• CAS: 136202-05-6
• 化学式: C₂₀H₁₈IO₃P
• 分子量: 464.239
• InChiKey: NBQKAASFZGREPL-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.6
• 重原子数：
  25
• 可旋转键数：
  5
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.1
• 拓扑面积：
  35.5
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  (3,6-dimethoxy-2-iodophenyl)diphenylphosphine oxide 在 三氯硅烷 、 铜 作用下， 以 N,N-二甲基甲酰胺 、 xylene 为溶剂， 反应 49.5h， 生成 [2-(2-diphenylphosphanyl-3,6-dimethoxyphenyl)-3,6-dimethoxyphenyl]-diphenylphosphane
  参考文献：
  名称：

  Synthesis, resolution and applications of 3,3′-bis(RO)-MeO-BIPHEP derivatives

  摘要：

  A series of optically pure 3,3'-bis(RO)-MeO-BIPHEP derivatives are prepared and used in palladium catalyzed asymmetric transformations. The phosphine oxide of (+/-)-5 is prepared in four steps from p-methoxyphenol and resolved using the novel resolving reagent chloro((L)-menthoxy)dimethylsilane. Subsequent conversions provide catalysts 8 and 9. Ligands 6, 7 and 10 are prepared in six steps from p-methoxyphenol and the phosphine oxides of 6 and 7, and 10 are resolved using di-p-toluoyl- and dibenzoyl-(L)-tartaric acid, respectively. (R)-3,3'-Bispivalate 8 is superior to the other catalysts in asymmetric Heck reaction with 2,3-dihydrofuran while (R)-(+)-bis(tolyloxy) 10 and (+)-(R)-sugar derivative 9 are better in the Pd-catalyzed polyene cyclization; however, the absolute sense of chirality in the product from the polyene cyclization was reversed to that obtained when (R)-(+)BINAP and (R)-(+)-MeO-BIPHEP were used. (C) 2004 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetlet.2004.03.073
• 作为产物：
  描述：

  (2,5-dimethoxyphenyl)diphenylphosphine oxide 在 lithium diisopropyl amide 、 碘 作用下， 以 四氢呋喃 、 正己烷 为溶剂， 反应 0.58h， 以75.5%的产率得到(3,6-dimethoxy-2-iodophenyl)diphenylphosphine oxide
  参考文献：
  名称：

  锰（III）介导的芳烃直接膦酰化

  摘要：

  锰（III）促进的单-和二取代的芳烃与亚磷酸二烷基酯的直接膦酰化反应可以很好地提供区域选择性的二烷基膦酸酯。该反应可适用于带有给电子基团和吸电子基团如酯和腈的芳烃。

  DOI：

  10.1016/j.tetlet.2010.03.029

文献信息

• Ortho substituted chiral phosphines and phosphinites and their use in asymmetric catalytic reactions
  申请人：The Penn State Research Foundation

  公开号：US20020128501A1

  公开（公告）日：2002-09-12

  3,3′-Substituted chiral biaryl phosphine and phosphinite ligands and metal complexes based on such chiral ligands useful in asymmetric catalysis are disclosed. The metal complexes are useful as catalysts in asymmetric reactions, such as, hydrogenation, hydride transfer, allylic alkylation, hydrosilylation, hydroboration, hydrovinylation, hydroformylation, olefin metathesis, hydrocarboxylation, isomerization, cyclopropanation, Diels-Alder reaction, Heck reaction, isomerization, Aldol reaction, Michael addition, epoxidation, kinetic resolution and [m+n] cycloaddition. The metal complexes are particularly effective in Ru-catalyzed asymmetric hydrogenation of beta-ketoesters to beta-hydroxyesters and Ru-catalyzed asymmetric hydrogenation of enamides to beta amino acids.

  揭示了基于3,3'-取代手性联苯膦和膦酸酯配体以及基于这种手性配体的金属配合物，在不对称催化中有用。这些金属配合物在不对称反应中作为催化剂很有用，例如氢化、氢化物转移、烯丙基烷基化、氢硅烷基化、氢硼烷基化、氢乙烯基化、氢甲酰基化、烯烃交换反应、羰基化、异构化、环丙烷化、Diels-Alder反应、Heck反应、醛缩反应、Michael加成、环氧化、动力学分辨和[m+n]环加成。这些金属配合物在Ru催化的不对称氢化β-酮酸酯为β-羟基酯和Ru催化的不对称氢化烯酰胺为β-氨基酸中特别有效。
• Selective ortho lithiation of (2,5-dimethoxyphenyl)diphenylphosphine oxide and trapping of the resulting aryllithium with electrophiles
  作者：John M. Brown、Simon Woodward

  DOI：10.1021/jo00024a019

  日期：1991.11

  The title compound undergoes predominant 6-lithiation, ortho to the methoxy and phosphinoyl groups, on reaction with t-BuLi in THF under conditions of thermodynamic control at low temperature. The organolithium compound is stable at least to 0-degree-C and can be trapped by a range of electrophiles to give the corresponding tetrasubstituted (diphenylphosphinoyl)arenes in moderate to good yield. The iodide formed by this sequence undergoes Ullman coupling to the diphenyl, which exhibits a novel restricted rotation phenomenon, in good yield under mild conditions. (2,5-Dimethoxyphenyl)diphenylphosphine sulfide lithiates exclusively at the 4-position under the same conditions, whilst the corresponding phosphine is unreactive.
• EP1341797A4
  申请人：——

  公开号：EP1341797A4

  公开（公告）日：2005-06-15
• ORTHO SUBSTITUTED CHIRAL PHOSPHINES AND PHOSPHINITES AND THEIR USE IN ASYMMETRIC CATAYLTIC REACTIONS
  申请人：THE PENN STATE RESEARCH FOUNDATION

  公开号：EP1341797A1

  公开（公告）日：2003-09-10
• US6653485B2
  申请人：——

  公开号：US6653485B2

  公开（公告）日：2003-11-25