1-phenylvinyl N,N-dimethylcarbamate | 762242-53-5

• 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: 1-phenylvinyl N,N-dimethylcarbamate
• 英文别名: 1-phenylvinyl dimethylcarbamate；1-phenylethenyl N,N-dimethylcarbamate
• CAS: 762242-53-5
• 化学式: C₁₁H₁₃NO₂
• 分子量: 191.23
• InChiKey: MKFREOPARBBEBJ-UHFFFAOYSA-N

物化性质

• 沸点：
  298.3±23.0 °C(Predicted)
• 密度：
  1.068±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.3
• 重原子数：
  14
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.18
• 拓扑面积：
  29.5
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  1-phenylvinyl N,N-dimethylcarbamate 在 四氢吡喃 、 silver hexafluoroantimonate 、 dichloro(pentamethylcyclopentadienyl)rhodium (III) dimer 、 三氟化硼乙醚 、 copper diacetate 作用下， 以 1,4-二氧六环 为溶剂， 反应 36.0h， 生成 6-phenyl-4-(prop-1-en-2-yl)-2H-pyran-2-one
  参考文献：
  名称：

  Rh(III)-Catalyzed C–H Activation with Allenes To Synthesize Conjugated Olefins

  摘要：

  Rh-III-catalyzed C-H activation with allenes produces highly unsaturated conjugated olefins. The reaction is applicable to both olefin and arene C(sp(2))-H and is compatible with a variety of functional groups. The products can be further transformed into other important skeletons through Diels-Alder reaction and intramolecular transesterification.

  DOI：

  10.1021/ol403407q
• 作为产物：
  描述：

  1-phenylethyl N,N-dimethylcarbamate 在 Ph(COD)2BF₄ 、 氢气 、 三苯基膦 作用下， 以 二氯甲烷 为溶剂， 生成 1-phenylvinyl N,N-dimethylcarbamate
  参考文献：
  名称：

  用单齿亚磷酰胺对映体选择性RH催化烯醇乙酸酯和烯醇氨基甲酸酯的氢化反应。

  摘要：

  [反应：见正文]单齿亚磷酰胺，特别是PipPhos及其八氢类似物，是铑催化芳族烯醇乙酸酯，烯醇氨基甲酸酯和2-二烯氨基甲酸酯的不对称氢化的极佳配体，ee高达98％ee。将这些后一种底物选择性地氢化为烯丙醇的氨基甲酸酯。

  DOI：

  10.1021/ol051559c

文献信息

• Rhodium‐Catalyzed Vinylic C–H Functionalization of Enol Carbamates with Maleimides
  作者：Satyasheel Sharma、Sang Hoon Han、Hyeim Jo、Sangil Han、Neeraj Kumar Mishra、Miji Choi、Taejoo Jeong、Jihye Park、In Su Kim

  DOI：10.1002/ejoc.201600558

  日期：2016.7

  The rhodium(III)-catalyzed direct C–H functionalization of enol carbamates with a range of maleimides is described. With the assistance of the carbamoyl directing group, this reaction provides biologically relevant succinimide compounds by proceeding through a C–Rh addition and subsequent protonation pathway.

  描述了铑 (III) 催化的烯醇氨基甲酸酯与一系列马来酰亚胺的直接 C-H 官能化。在氨基甲酰基导向基团的帮助下，该反应通过 C-Rh 加成和随后的质子化途径提供生物相关的琥珀酰亚胺化合物。
• Nickel-Catalyzed Efficient and Practical Suzuki−Miyaura Coupling of Alkenyl and Aryl Carbamates with Aryl Boroxines
  作者：Li Xu、Bi-Jie Li、Zhen-Hua Wu、Xing-Yu Lu、Bing-Tao Guan、Bi-Qin Wang、Ke-Qing Zhao、Zhang-Jie Shi

  DOI：10.1021/ol9029534

  日期：2010.2.19

  Suzuki−Miyaura coupling of unactivated alkenyl carbamates is described to construct polysubstituted olefins. The developed process is also suitable for heteroaromatic and even electron-rich aromatic carbamates.

  未活化的烯基氨基甲酸酯的Suzuki-Miyaura偶联被描述为构建多取代的烯烃。所开发的方法还适用于杂芳族甚至是富电子的芳族氨基甲酸酯。
• [EN] BIDENTATE SECONDARY PHOSPHINE OXIDE CHIRAL LIGANDS FOR USE IN ASYMMETRIC ADDITION REACTIONS<br/>[FR] LIGANDS CHIRAUX BIDENTATES LIÉS À UN OXYDE DE PHOSPHINE SECONDAIRE ET LEUR UTILISATION DANS DES RÉACTIONS D'ADDITION ASYMÉTRIQUE
  申请人：SOLVIAS AG

  公开号：WO2009065783A1

  公开（公告）日：2009-05-28

  Compounds of the formula I, in the form of mixtures comprising predominantly one enantiomer or in the form of pure enantiomers, secondary phosphine-Q-P*(=O)HR1 (I) in which secondary phosphine is a C-bonded, secondary phosphine group -P(R) 2; in which R is in each case independently hydrocarbon radicals or heterohydrocarbon radicals; Q is a bivalent, achiral, aromatic base skeleton, a bivalent, achiral ferrocene base skeleton, an optionally substituted bivalent cycloalkane or heterocycloalkane skeleton, or a C 1-C 4-alkylene skeleton, and in which base skeletons a secondary phosphine group is bonded directly to a carbon atom, or, in the case of cyclic base skeletons, directly to a carbon atom or via a C1-C 4-alkylene group, and in which base skeletons a P-chiral group -P*(O)HR1 is bonded to a carbon atom such that the phosphorus atoms are linked via 1 to 7 atoms of a carbon chain optionally interrupted by heteroatoms from the group of O, S, N, Fe or Si; P* is a chiral phosphorus atom; and R1 is a hydrocarbon radical, a C-bonded heterohydrocarbon radical or a ferrocenyl radical, with the proviso that R1 is an achiral ferrocenyl radical when Q is an achiral ferrocenyl base skeleton. Metal complexes of these ligands in a molarratio of ligand to metal of about 1.3:1 to 0.9:1are homogeneous catalysts for asymmetric addition reactions, particularly hydrogenations.

  公式I的化合物以纯对映体形式或以主要含有一种对映体的混合物的形式存在，其中二级膦-Q-P *（= O）HR1（I）中的二级膦是C-键结的二级膦基团-P（R）2;其中R分别是烃基或杂原子烃基；Q是二价的、不手性的、芳香基骨架、二价的、不手性的二茂铁基骨架、可选取代的二价环烷烃或杂环烷烃骨架，或C1-C4-烷基骨架，在这些基骨架中，二级膦基团直接键合到碳原子上，或在环状基骨架的情况下，直接键合到碳原子或通过C1-C4-烷基链键合，其中在这些基骨架中，P-手性基团-P *（O）HR1 键合到碳原子，使得磷原子通过由O、S、N、Fe或Si组成的杂原子随意中断的1到7个碳链原子链接；P *是手性磷原子；R1是烃基、C-键结的杂原子烃基或二茂铁基基团，但当Q是不手性的二茂铁基骨架时，R1是不手性的二茂铁基基团。这些配体的金属配合物在配体与金属的摩尔比约为1.3:1至0.9:1的情况下是对称加成反应的均相催化剂，特别是氢化反应。
• BIDENTATE SECONDARY PHOSPHINE OXIDE CHIRAL LIGANDS FOR USE IN ASYMMETRIC ADDITION REACTIONS
  申请人：Pugin Benoît

  公开号：US20110098485A1

  公开（公告）日：2011-04-28

  Compounds of the formula I, in the form of mixtures comprising predominantly one enantiomer or in the form of pure enantiomers, secondary phosphine-Q-P*(═O)HR 1 (I) in which secondary phosphine is a C-bonded, secondary phosphine group —P(R) 2 ; in which R is in each case independently hydrocarbon radicals or heterohydrocarbon radicals; Q is a bivalent, achiral, aromatic base skeleton, a bivalent, achiral ferrocene base skeleton, an optionally substituted bivalent cycloalkane or heterocycloalkane skeleton, or a C1-C4-alkylene skeleton, and in which base skeletons a secondary phosphine group is bonded directly to a carbon atom, or, in the case of cyclic base skeletons, directly to a carbon atom or via a C 1 -C 4 -alkylene group, and in which base skeletons a P-chiral group —P*(O)HR 1 is bonded to a carbon atom such that the phosphorus atoms are linked via 1 to 7 atoms of a carbon chain optionally interrupted by heteroatoms from the group of O, S, N, Fe or Si; P* is a chiral phosphorus atom; and R 1 is a hydrocarbon radical, a C-bonded heterohydrocarbon radical or a ferrocenyl radical, with the proviso that R 1 is an achiral ferrocenyl radical when Q is an achiral ferrocenyl base skeleton. Metal complexes of these ligands in a molar ratio of ligand to metal of about 1.3:1 to 0.9:1 are homogeneous catalysts for asymmetric addition reactions, particularly hydrogenations.

  化合物I的公式，以主要由一对映异体组成的混合物形式或纯映异体形式存在，其中二级膦-Q-P*（═O）HR1（I），其中二级膦是C-键合的二级膦基团-P（R）2；其中R在每种情况下独立地是碳氢基团或杂环碳氢基团；Q是二价的、无手性的、芳香基骨架、二价的、无手性的二茂铁基骨架、可选取代的二价环烷基或杂环烷基骨架，或C1-C4-烷基骨架，在这些基骨架中，一个二级膦基团直接键合到碳原子上，或在环状基骨架的情况下，直接键合到碳原子或通过C1-C4-烷基骨架，且在这些基骨架中，一个P-手性基团-P*（O）HR1键合到碳原子，使得磷原子通过1到7个碳链原子（可选取自O、S、N、Fe或Si的杂原子组）连接；P*是一个手性磷原子；R1是一个碳氢基团、C-键合的杂环碳氢基团或二茂铁基基团，但当Q是无手性二茂铁基骨架时，R1是一个无手性二茂铁基基团。这些配体的金属配合物在配体与金属的摩尔比约为1.3:1至0.9:1时，是不对称加成反应的均相催化剂，特别是氢化反应。
• Enantioselective rhodium-catalyzed hydrogenation of enol carbamates in the presence of monodentate phosphines
  作者：Stephan Enthaler、Giulia Erre、Kathrin Junge、Dirk Michalik、Anke Spannenberg、Fabrizio Marras、Serafino Gladiali、Matthias Beller

  DOI：10.1016/j.tetasy.2007.06.001

  日期：2007.6

  The rhodium-catalyzed asymmetric hydrogenation of different acyclic and cyclic enol carbarnates to give optically active carbarnates has been examined in the presence of chiral monodentate ligands based on a 4,5-dihydro-3H-dinaphthophosphepine motif 4. The enantioselectivity is largely dependent upon the reaction conditions, the nature of substituents on the phosphorus ligand and structure of the enol carbamate. By applying the optimized reaction conditions, enantioselectivities of up to 96% ee have been achieved. (c) 2007 Elsevier Ltd. All rights reserved.