6-((diphenylphosphino)methyl)-2,2'-bipyridine | 1373719-31-3

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡啶及其衍生物
• 英文名称: 6-((diphenylphosphino)methyl)-2,2'-bipyridine
• 英文别名: 6-di-phenyphosphinomethyl-2,2'-bipyridine；6-[(diphenylphosphino)methyl]-2,2’-bipyridine；6-Diphenylphosphinomethyl-2,2'-bipyridine；diphenyl-[(6-pyridin-2-ylpyridin-2-yl)methyl]phosphane
• CAS: 1373719-31-3
• 化学式: C₂₃H₁₉N₂P
• 分子量: 354.391
• InChiKey: ZHNKHDWCHZVGGS-UHFFFAOYSA-N

物化性质

• 沸点：
  506.0±45.0 °C(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4.1
• 重原子数：
  26
• 可旋转键数：
  5
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.04
• 拓扑面积：
  25.8
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  五羰基铁 、 6-((diphenylphosphino)methyl)-2,2'-bipyridine 以 1,4-二氧六环 为溶剂， 反应 26.0h， 以95%的产率得到(6-[(diphenylphosphino)methyl]-2,2’-bipyridine)Fe(CO)₂
  参考文献：
  名称：

  具有联吡啶C和联吡啶短C的联吡啶基PNN钳配体的二羰基铁配合物？C键长度：无毒或无毒配体？

  摘要：

  合成了一系列具有联吡啶基PNN钳位配体的二羰基铁配合物，并通过多核NMR光谱（1 H，13 C，15 N，31 P），IR光谱，循环伏安法，57 FeMössbauer光谱，XPS光谱和单晶X射线衍射。通式为[（R-PNN）Fe（CO）2 ]的配合物（5：R-PNN = t Bu-PNN = 6-[[（叔丁基膦基）甲基] -2,2'-联吡啶，6：R-PNN = i Pr-PNN = 6-[[（二异丙基膦基）甲基] -2,2'-联吡啶和7：R-PNN = Ph-PNN = 6-[（（二苯基膦基）甲基] -2,2'-联吡啶）具有不同的P-取代的PNN钳形配体。配合物5和6是通过还原相应的二卤化物配合物[（R-PNN）Fe（X）2 ]（1：R = t Bu，X = Cl; 2：R = t Bu，X = Br; 3： R = i Pr，X = Cl; 4：R = i Pr，X = Br）在CO存在

  DOI：

  10.1002/chem.201304631
• 作为产物：
  描述：

  6-(chloromethyl)-2,2'-bipyridine 、 二苯基膦 在 potassium tert-butylate 作用下， 以 四氢呋喃 、 乙醚 为溶剂， 反应 1.17h， 以61%的产率得到6-((diphenylphosphino)methyl)-2,2'-bipyridine
  参考文献：
  名称：

  联吡啶钌基钳式配合物催化伯醇与仲胺的脱氢偶联形成叔酰胺和二氢

  摘要：

  在中性条件下（对于脱芳烃化的配合物），基于联吡啶的钌钳配合物（0.2-1 mol％）有效地催化了伯醇与仲胺的脱氢偶联反应，形成叔酰胺和二氢（H 2）。催化量的碱。该反应对位阻敏感。在笨重的仲胺酰胺化的情况下，空间位阻较少的配合物更有效。还证明了在仲胺存在下对伯胺的选择性酰化。

  DOI：

  10.1002/adsc.201300620

文献信息

• Dehydrogenative Cross-Coupling of Primary Alcohols To Form Cross-Esters Catalyzed by a Manganese Pincer Complex
  作者：Uttam Kumar Das、Yehoshoa Ben-David、Gregory Leitus、Yael Diskin-Posner、David Milstein

  DOI：10.1021/acscatal.8b04585

  日期：2019.1.4

  products, liberating hydrogen gas, is reported. The reaction is catalyzed by a pincer complex of earth-abundant manganese in the presence of catalytic base, without any hydrogen acceptor or oxidant. Mechanistic insight indicates that a dearomatized complex is the actual catalyst, and indeed this independently prepared dearomatized complex catalyzes the reaction under neutral conditions.

  据报道，伯醇的贱金属催化脱氢交叉偶联形成交叉酯为主要产物，释放出氢气。该反应是在没有任何氢受体或氧化剂的情况下，在催化剂碱的存在下，由富含地球的锰的夹杂物络合物催化的。机械学的见解表明脱芳香化的络合物是实际的催化剂，并且实际上，这种独立制备的脱芳香化的络合物在中性条件下催化了反应。
• Synthesis, Structures, and Dearomatization by Deprotonation of Iron Complexes Featuring Bipyridine-based PNN Pincer Ligands
  作者：Thomas Zell、Robert Langer、Mark A. Iron、Leonid Konstantinovski、Linda J. W. Shimon、Yael Diskin-Posner、Gregory Leitus、Ekambaram Balaraman、Yehoshoa Ben-David、David Milstein

  DOI：10.1021/ic401432m

  日期：2013.8.19

  iron(II) chloride and bromide. These reactions lead to the formation of two types of complexes: mono-chelated neutral complexes of the type [(R-PNN)Fe(X)2] and bis-chelated dicationic complexes of the type [(R-PNN)2Fe]2+. The complexes [(R-PNN)Fe(X)2] (1: R = tBu, X = Cl, 2: R = tBu, X = Br, 3: R = iPr, X = Cl, and 4: R = iPr, X = Br) are readily prepared from reactions of FeX2 with the free R-PNN ligand in

  报道了具有基于联吡啶的PNN配体的新型铁钳复合物的合成和表征。三个膦取代的钳位配体，即已知的t Bu-PNN（6-（（二叔丁基膦基甲基）甲基）-2,2'-联吡啶）和两个新的i Pr-PNN（6-（（di -异-propylphosphino）甲基）-2,2'-联吡啶）和PH-PNN（6 - （（二苯基膦基）甲基）-2,2'-联吡啶配位体被合成并与铁研究了连接反应）（II），氯化和溴化物。这些反应导致两种类型的复合物的形成：单-chelated类型的中性配合物[（R-PNN）的Fe（X）2 ]和二类型的-chelated双阳离子配合物[（R-PNN）2Fe] 2+。络合物[（R-PNN）Fe（X）2 ]（1：R = t Bu，X = Cl，2：R = t Bu，X = Br，3：R = i Pr，X = Cl，和4：R =我镨，X = Br的）很容易从FEX的反应制备2：1的比例与游离R-P
• Bis(tridentate) Iron(II) Complexes with a Cyclometalating Unit: Photophysical Property Enhancement with Combinatorial Strong Ligand Field Effect
  作者：Zhou Tang、Xiao-Yong Chang、Qingyun Wan、Jian Wang、Chensheng Ma、Kwok-Chung Law、Yungen Liu、Chi-Ming Che

  DOI：10.1021/acs.organomet.0c00149

  日期：2020.8.10

  reactions of [FeII(C∧Npy∧Npy)Br(PMe3)2] (1, HC∧Npy∧Npy = 6-(phenyl)-2,2′-bipyridine) and [FeII(C∧Nppy∧Nisoquin)Br(PMe3)2] (2, HC∧Nppy∧Nisoquin = 3-(4,6-diphenylpyridin-2-yl)isoquinoline) with tridentate ligands L, affording [FeII(C∧Npy∧Npy)(4′-R-tpy)]+ (3a–e, R = H, Cl, p-ClC6H4, p-MeOC6H4, p-tol, respectively; tpy = 2,2′:6′,2″-terpyridine), [FeII(C∧Nppy∧Nisoquin)(tpy)]+ (4), [FeII(C∧Npy∧Npy)(6-(Ph2PCH2)-bpy)]+

  一系列的双（三齿）环金属oligopyridine络合物的[Fe II（C ∧ Ñ ∧ N）（L）] +已通过的的[Fe的反应合成II（C ∧ Ñ PY ∧ Ñ PY）溴（PME 3）2 ]（1，HC ∧ ñ PY ∧ ñ PY = 6-（苯基）-2,2'-联吡啶）和[铁II（C ∧ ñ PPY ∧ ñ isoquin）溴（PME 3）2 ]（2，HC ∧Ñ PPY ∧ Ñ isoquin = 3-（4,6-二苯基吡啶-2-基）异喹啉）具有三齿配体L，得到的[Fe II（C ∧ Ñ PY ∧ Ñ PY）（4'- R-TPY）] +（图3a - ë，R = H，氯，p -ClC 6 ħ 4，p -MeOC 6 ħ 4，p分别-tol; TPY = 2,2'：6'，2“ -三联吡啶），的[Fe II（ ç ∧ ñ PPY ∧ ñ isoquin）（TPY）] +（4），的[Fe II（C ∧ Ñ
• Ruthenium complexes and their uses in processes for formation and/or hydrogenation of esters, amides and derivatives thereof
  申请人：Milstein David

  公开号：US09045381B2

  公开（公告）日：2015-06-02

  The present invention relates to novel Ruthenium catalysts and related borohydride complexes, and the use of such catalysts, inter alia, for (1) hydrogenation of amides (including polyamides) to alcohols and amines; (2) preparing amides from alcohols with amines (including the preparation of polyamides (e.g., polypeptides) by reacting dialcohols and diamines and/or by polymerization of amino alcohols); (3) hydrogenation of esters to alcohols (including hydrogenation of cyclic esters (lactones) or cyclic di-esters (di-lactones) or polyesters); (4) hydrogenation of organic carbonates (including polycarbonates) to alcohols and hydrogenation of carbamates (including polycarbamates) or urea derivatives to alcohols and amines; (5) dehydrogenative coupling of alcohols to esters; (6) hydrogenation of secondary alcohols to ketones; (7) amidation of esters (i.e., synthesis of amides from esters and amines); (8) acylation of alcohols using esters; (9) coupling of alcohols with water to form carboxylic acids; and (10) dehydrogenation of beta-amino alcohols to form pyrazines. The present invention further relates to the novel uses of certain pyridine Ruthenium catalysts.

  本发明涉及新型钌催化剂及相关硼氢化物络合物的使用，其中包括以下用途：(1)将酰胺（包括聚酰胺）加氢成为醇和胺；(2)通过醇和胺制备酰胺（包括通过双醇和双胺反应制备聚酰胺（例如多肽）和通过氨基醇聚合制备聚酰胺）；(3)将酯加氢成为醇（包括环酯（内酯）或环二酯（内二酯）或聚酯的加氢）；(4)将有机碳酸酯（包括聚碳酸酯）加氢成为醇和将氨基甲酸酯（包括聚氨基甲酸酯）或脲衍生物加氢成为醇和胺；(5)将醇脱氢偶合成酯；(6)将二级醇加氢成为酮；(7)酯胺化（即从酯和胺合成酰胺）；(8)使用酯对醇进行酰化；(9)将醇与水偶联形成羧酸；以及(10)将β-氨基醇脱氢成为吡嗪。本发明还涉及某些吡啶钌催化剂的新型用途。
• NOVEL RUTHENIUM COMPLEXES AND THEIR USES IN PROCESSES FOR FORMATION AND/OR HYDROGENATION OF ESTERS, AMIDES AND DERIVATIVES THEREOF
  申请人：Milstein David

  公开号：US20130281664A1

  公开（公告）日：2013-10-24

  The present invention relates to novel Ruthenium catalysts and related borohydride complexes, and the use of such catalysts, inter alia, for (1) hydrogenation of amides (including polyamides) to alcohols and amines; (2) preparing amides from alcohols with amines (including the preparation of polyamides (e.g., polypeptides) by reacting dialcohols and diamines and/or by polymerization of amino alcohols); (3) hydrogenation of esters to alcohols (including hydrogenation of cyclic esters (lactones) or cyclic di-esters (di-lactones) or polyesters); (4) hydrogenation of organic carbonates (including polycarbonates) to alcohols and hydrogenation of carbamates (including polycarbamates) or urea derivatives to alcohols and amines; (5) dehydrogenative coupling of alcohols to esters; (6) hydrogenation of secondary alcohols to ketones; (7) amidation of esters (i.e., synthesis of amides from esters and amines); (8) acylation of alcohols using esters; (9) coupling of alcohols with water to form carboxylic acids; and (10) dehydrogenation of beta-amino alcohols to form pyrazines. The present invention further relates to the novel uses of certain pyridine Ruthenium catalysts.

  本发明涉及新型钌催化剂和相关硼氢化物配合物，以及使用这些催化剂，包括：（1）将酰胺（包括聚酰胺）加氢为醇和胺；（2）用胺从醇制备酰胺（包括通过二元醇和二胺反应或氨基醇聚合制备聚酰胺（例如聚肽））；（3）将酯加氢为醇（包括环酯（内酯）或环二酯（二内酯）或聚酯的加氢）；（4）将有机碳酸酯（包括聚碳酸酯）加氢为醇和将氨基甲酸酯（包括聚氨基甲酸酯）或脲衍生物加氢为醇和胺；（5）醇的脱氢缩合成酯；（6）将二级醇加氢为酮；（7）酯的酰胺化（即从酯和胺合成酰胺）；（8）使用酯对醇进行酰化；（9）将醇与水偶联形成羧酸；以及（10）β-氨基醇的脱氢缩合形成吡嗪的新用途。本发明还涉及某些吡啶基钌催化剂的新用途。