N,N,N',N'-tetraethyl-P-(3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)phosphonicdiamide

• 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: N,N,N',N'-tetraethyl-P-(3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)phosphonicdiamide
• 英文别名: N,N,N',N'-tetraethyl-P-(3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)phosphonic diamide；N-[diethylamino-[3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl]phosphoryl]-N-ethylethanamine
• 化学式: C₂₀H₃₆BN₂O₃P
• 分子量: 394.302
• InChiKey: CMPQCNHUZWRKMY-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.49
• 重原子数：
  27
• 可旋转键数：
  8
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.7
• 拓扑面积：
  42
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  N,N,N',N'-tetraethyl-P-(3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)phosphonicdiamide 在 copper(ll) bromide 作用下， 以 甲醇 、 水 为溶剂， 反应 4.0h， 以26 mg的产率得到N,N,N',N'-tetraethyl-P-(3-(bromo)phenyl)phosphonic diamide
  参考文献：
  名称：

  氢键控制的正式元多取代芳烃-选择性C-H变换和区域选择性合成

  摘要：

  所述元-选择性官能团引入到芳族底物已经成功地由氢键控制实现的元-选择性C-H硼化和氧硼基为其它官能团的连续转化。通过这种方法，可以引入广泛的官能团而无需分离硼化的中间体。所期望的元-官能化在一锅的方式获得即使是在克规模的芳族产物。还实现了多取代芳族化合物的区域选择性合成。

  DOI：

  10.1021/acs.orglett.9b00030
• 作为产物：
  描述：

  N,N,N’,N’-tetraethyl-P-phenyl-phosphonic diamide 、 联硼酸频那醇酯 在 (1,5-cyclooctadiene)(methoxy)iridium(I) dimer 、 1-(2-([2,2'-bipyridin]-5-yl)phenyl)-3-cyclohexylurea 作用下， 以 对二甲苯 为溶剂， 反应 16.0h， 生成 N,N,N',N'-tetraethyl-P-(3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)phosphonicdiamide
  参考文献：
  名称：

  氢键控制的正式元多取代芳烃-选择性C-H变换和区域选择性合成

  摘要：

  所述元-选择性官能团引入到芳族底物已经成功地由氢键控制实现的元-选择性C-H硼化和氧硼基为其它官能团的连续转化。通过这种方法，可以引入广泛的官能团而无需分离硼化的中间体。所期望的元-官能化在一锅的方式获得即使是在克规模的芳族产物。还实现了多取代芳族化合物的区域选择性合成。

  DOI：

  10.1021/acs.orglett.9b00030

文献信息

• BIPYRIDYL COMPOUND
  申请人：JAPAN SCIENCE AND TECHNOLOGY AGENCY

  公开号：US20170001960A1

  公开（公告）日：2017-01-05

  There are provided a compound capable of being a novel ligand allowing regioselective borylation to be performed in the aromatic borylation reaction, and a catalyst using the same compound. There is provided a bipyridyl compound represented by a general formula ( 1 ): (wherein A represents a single bond, a vinylene group or an ethynylene group; X represents an oxygen atom or a sulfur atom; n pieces of R 1 may be the same or different, and R 1 represents a hydrogen atom, a halogen atom, an optionally substituted hydrocarbon group, an optionally substituted alkoxy group, an optionally substituted aryloxy group, an optionally substituted amino group, a cyano group, a nitro group, or an alkoxycarbonyl group, or two adjacent R 1 may form a saturated or unsaturated ring structure optionally containing a hetero atom together with the carbon atoms bonded to the two R 1 ; R 2 represents a hydrogen atom, an optionally substituted hydrocarbon group, an optionally substituted alkoxy group, or an optionally substituted aryloxy group; and n represents a number of 1 to 4 ).

  提供了一种化合物，可以作为一种新型配体，在芳基硼化反应中实现区域选择性硼化，并提供了使用该化合物的催化剂。提供了一种由通式（1）表示的双吡啶化合物：（其中A代表单键、乙烯基或乙炔基；X代表氧原子或硫原子；n个R1可能相同或不同，R1代表氢原子、卤素原子、可选择取代的碳氢基团、可选择取代的烷氧基团、可选择取代的芳氧基团、可选择取代的氨基团、氰基、亚硝基或烷氧羰基，或者两个相邻的R1可能形成一个饱和或不饱和环结构，该环结构与两个R1键合的碳原子一起可能含有一个杂原子；R2代表氢原子、可选择取代的碳氢基团、可选择取代的烷氧基团或可选择取代的芳氧基团；n代表1到4的数字）。
• A meta-selective C–H borylation directed by a secondary interaction between ligand and substrate
  作者：Yoichiro Kuninobu、Haruka Ida、Mitsumi Nishi、Motomu Kanai

  DOI：10.1038/nchem.2322

  日期：2015.9

  Regioselective C–H bond transformations are potentially the most efficient method for the synthesis of organic molecules. However, the presence of many C–H bonds in organic molecules and the high activation barrier for these reactions make these transformations difficult. Directing groups in the reaction substrate are often used to control regioselectivity, which has been especially successful for the ortho-selective functionalization of aromatic substrates. Here, we describe an iridium-catalysed meta-selective C–H borylation of aromatic compounds using a newly designed catalytic system. The bipyridine-derived ligand that binds iridium contains a pendant urea moiety. A secondary interaction between this urea and a hydrogen-bond acceptor in the substrate places the iridium in close proximity to the meta-C–H bond and thus controls the regioselectivity. 1H NMR studies and control experiments support the participation of hydrogen bonds in inducing regioselectivity. Reversible direction of the catalyst through hydrogen bonds is a versatile concept for regioselective C–H transformations. Directing groups in a substrate are frequently used to direct the regioselectivity of C–H activation reactions. Now it has been shown that regioselectivity can be directed by a ligand, which binds to both the catalysing metal centre and a distal hydrogen-bond acceptor in the substrate. This secondary interaction places the metal in close proximity to the reacting C–H bond.

  区域选择性C-H键转化可能是合成有机分子最有效的方法。然而，由于有机分子中存在许多C-H键以及这些反应的高活化能障碍，这些转化变得困难。反应底物中常常使用导向基团来控制区域选择性，这在芳香族底物的邻位选择性功能化方面取得了特别成功。在此，我们描述了一种使用新设计的催化体系对芳香化合物进行铱催化间位选择性C-H硼化的方法。与铱配位的双吡啶衍生物配体含有一个悬挂的脲部分。该脲与底物中氢键受体之间的次级相互作用使得铱靠近间位C-H键，从而控制了区域选择性。1H核磁共振研究和对照实验支持氢键在诱导区域选择性中的参与。通过氢键的可逆导向催化剂是区域选择性C-H转化的一个多功能概念。底物中的导向基团经常被用来引导C-H活化反应的区域选择性。现在已证明，配体可以通过与催化金属中心和底物中远端的氢键受体结合来导向区域选择性。这种次级相互作用使得金属靠近反应的C-H键。
• Hydrogen-Bond-Controlled Formal <i>Meta</i>-Selective C–H Transformations and Regioselective Synthesis of Multisubstituted Aromatic Compounds
  作者：Jie Wang、Takeru Torigoe、Yoichiro Kuninobu

  DOI：10.1021/acs.orglett.9b00030

  日期：2019.3.1

  The meta-selective introduction of functional groups into aromatic substrates was successfully achieved by hydrogen-bond-controlled meta-selective C–H borylation and successive conversion of the boryl group to other functional groups. By this method a wide range of functional groups could be introduced without isolation of the borylated intermediates. The desired meta-functionalized aromatic products

  所述元-选择性官能团引入到芳族底物已经成功地由氢键控制实现的元-选择性C-H硼化和氧硼基为其它官能团的连续转化。通过这种方法，可以引入广泛的官能团而无需分离硼化的中间体。所期望的元-官能化在一锅的方式获得即使是在克规模的芳族产物。还实现了多取代芳族化合物的区域选择性合成。