CN103071533A - Pb(Ni1/3Nb2/3)O3 (PNN) ligand-iron complex catalyst and preparation method and application thereof - Google Patents

Pb(Ni1/3Nb2/3)O3 (PNN) ligand-iron complex catalyst and preparation method and application thereof Download PDF

Info

Publication number
CN103071533A
CN103071533A CN2013100442479A CN201310044247A CN103071533A CN 103071533 A CN103071533 A CN 103071533A CN 2013100442479 A CN2013100442479 A CN 2013100442479A CN 201310044247 A CN201310044247 A CN 201310044247A CN 103071533 A CN103071533 A CN 103071533A
Authority
CN
China
Prior art keywords
pnn
iron complex
hydroboration
cdcl
nmr
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN2013100442479A
Other languages
Chinese (zh)
Inventor
黄正
张雷
彭东杰
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Shanghai Institute of Organic Chemistry of CAS
Original Assignee
Shanghai Institute of Organic Chemistry of CAS
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Shanghai Institute of Organic Chemistry of CAS filed Critical Shanghai Institute of Organic Chemistry of CAS
Priority to CN2013100442479A priority Critical patent/CN103071533A/en
Publication of CN103071533A publication Critical patent/CN103071533A/en
Priority to CN201410007219.4A priority patent/CN103962183B/en
Priority to PCT/CN2014/072159 priority patent/WO2014117752A1/en
Pending legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
    • C07F5/02—Boron compounds
    • C07F5/025—Boronic and borinic acid compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
    • B01J31/189—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms containing both nitrogen and phosphorus as complexing atoms, including e.g. phosphino moieties, in one at least bidentate or bridging ligand
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
    • C07F15/02—Iron compounds
    • C07F15/025—Iron compounds without a metal-carbon linkage
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
    • C07F15/06—Cobalt compounds
    • C07F15/065—Cobalt compounds without a metal-carbon linkage
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/30—Addition reactions at carbon centres, i.e. to either C-C or C-X multiple bonds
    • B01J2231/32—Addition reactions to C=C or C-C triple bonds
    • B01J2231/323—Hydrometalation, e.g. bor-, alumin-, silyl-, zirconation or analoguous reactions like carbometalation, hydrocarbation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
    • B01J2531/0238—Complexes comprising multidentate ligands, i.e. more than 2 ionic or coordinative bonds from the central metal to the ligand, the latter having at least two donor atoms, e.g. N, O, S, P
    • B01J2531/0241—Rigid ligands, e.g. extended sp2-carbon frameworks or geminal di- or trisubstitution
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/80—Complexes comprising metals of Group VIII as the central metal
    • B01J2531/84—Metals of the iron group
    • B01J2531/842—Iron
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/80—Complexes comprising metals of Group VIII as the central metal
    • B01J2531/84—Metals of the iron group
    • B01J2531/845—Cobalt

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Catalysts (AREA)

Abstract

The invention discloses a Pb(Ni1/3Nb2/3)O3 (PNN) ligand-iron complex catalyst and a preparation method and application thereof. The catalyst is a compound with a general formula shown in the specification. In the general formula, R refers to an alkane group of C1-C30 or an alkane of C6-C30, and X refers to a halogen atom. The catalyst is prepared by performing a complexing reaction between a PNN ligand and FeX2. The PNN ligand-iron complex catalyst disclosed by the invention is good in catalytic activity on a hydroboration reaction of monoolefine and not only is high in selectivity and high in yield but also is mild in reaction condition. Moreover, the preparation method for the PNN ligand-iron complex catalyst is simple, is friendly to the environment, mild in reaction condition, higher in yield, simple in postprocessing and is easy for mass production, and raw materials are low in cost and can be easily got.

Description

A kind of PNN part-iron complex Catalysts and its preparation method and application
Technical field
The present invention relates to a kind of PNN part-iron complex Catalysts and its preparation method and application, specifically, relate to a kind of iron complex Catalysts and its preparation method and its application in the hydroboration of monoolefine that contains to three flute profile PNN parts of electronics, belong to technical field of organic chemistry.
Background technology
Organic boronic and derivative Chang Zuowei intermediate thereof are widely used in the organic synthesis, such as, the Suzuki-Miyaura reaction just can be with organoboron compound C (sp 3) form the C-C key with the halogenated hydrocarbons coupling.Organic boronic acid derivative is compared with other organic metal nucleopilic reagent has unique stability, and many borates just can separation and purification and storage in air.Scientists has developed the method for multiple synthetic organic boric acid ester.Wherein a kind of method commonly used is that halogenated hydrocarbons is converted into organolithium reagent or RMgBr, the organometallic reagent that generates reacts to prepare organic boric acid ester with the compound of boracic again, but this method is because functional group's poor compatibility, generate again a large amount of inorganic salts in the course of reaction, not very high synthetic value.Recently, the people such as Hartwig have been developed a kind of Rh of using as catalyst, alkane and B 2Pin 2Reaction directly generates the method for organic boric acid ester, but reaction condition is relatively harsh.Not long ago Liu, the people such as Marder and Steel have reported again a kind of relative gentle method, they make catalyst with copper, halogenated hydrocarbons and B 2Pin 2Reaction generates organic boric acid ester, yet this method needs excessive B 2Pin 2, and have a large amount of inorganic salts to produce.
In addition, organic boric acid ester can prepare by Rh or Ir catalyzed alkene hydroboration.Although dialkyl group boron can be with directly addition of alkene, the dialkoxy borine is not having under the catalyst condition, reacts very slow.The hydroboration of metal catalytic can occur under very gentle condition, and has very high Atom economy, is a kind of effective synthesizing mean.Such as, the Wilkinson catalyst has been widely used in the hydroboration of multiple alkene, but usually follows multiple side reaction, such as the reaction of alkene dehydrogenation boronation, hydrogenation etc.Another weak point is that when particularly using the pinacol borine as borane reagent, regioselectivity is relatively poor in aryl ethylene hydroboration process.Secondly, the purity of Wilkinson catalyst has a significant impact reactivity, and action need is careful especially.Moreover, in many reactions, for the conversion ratio that obtains, need to add more Rh and the catalyst of this class costliness of Ir.
Because the noble metal reserves are few, expensive, and for the consideration of environment aspect, in the last few years, scientists was attempted to substitute noble metal with abundant, the cheap base metal of reserves on the earth and was used for organic catalytic reaction.In in the past 10 years, the complex compound of iron is subject to extensive concern in the homogeneous catalysis field.Recently, the people such as Ritter have reported the complex compound of iron of '-imine pyridinyl part to 1, and the hydroboration of 3-diene has preferably active (J.Am.Chem.Soc.2009,131,12915).But contain to the iron complex of three flute profile PNN parts of electronics and as catalyst being applied in the hydroboration of more common monoolefine and there is not yet so far any report.
Summary of the invention
The purpose of this invention is to provide a kind of PNN part-iron complex Catalysts and its preparation method and application, be the iron complex catalyst that catalyst field increases a kind of cheap, environmental friendliness, 100% atom validity, gentle reaction condition, simple separation method, good functional group is compatible and the hydroboration of monoolefine is had excellent activity.
PNN part of the present invention-iron complex catalyst is the compound with following general formula:
Figure BDA00002817796800021
R in the general formula is C 1～C 30Alkyl or C 6～C 30Aryl; X in the general formula is halogen atom.
As a kind of preferred version, the R in the general formula is selected from ethyl, isopropyl, the tert-butyl group or phenyl; X in the general formula is selected from Cl, Br or I.
A kind of method for preparing above-mentioned PNN part-iron complex catalyst is with PNN part and FeX 2Carry out complexation reaction, reaction expression is as follows:
R in the general formula and X's is described as defined above.
As a kind of preferred version, the operation of described complexation reaction comprises the steps:
A) preparation FeX 2Tetrahydrofuran solution and the tetrahydrofuran solution of PNN part;
B) be controlled under 20～30 ℃, the tetrahydrofuran solution of PNN part is dropwise added FeX 2Tetrahydrofuran solution in;
C) drip and finish, at room temperature stirring reaction;
D) reaction finishes, and concentrated dried solvent carries out the purifying post processing.
As further preferred version, FeX 2The molar concentration of tetrahydrofuran solution be 0.01 mol/L～0.1 mol/L; The molar concentration of the tetrahydrofuran solution of PNN part is 0.1 mol/L～1.0 mol/L; PNN part and FeX 2Mol ratio be 1:1～2:1.
As further preferred version, described purifying post processing comprises the steps:
E) will concentrate the gained solid and be dissolved in the carrene, then add ether, and make and separate out solid;
F filters, and filter cake washs with ether, gets brick-red powder;
G) the brick-red powder of gained is dissolved in the mixed solvent that is formed by the 1:1 volume ratio by carrene and n-hexane, leaves standstill and make crystallization;
H) collect red crystals.
The application of a kind of described PNN part-iron complex catalyst is the catalyst as the hydroboration of monoolefine.
As a kind of preferred version, the hydroboration of described monoolefine refers to only occur the hydroboration of the two keys in α position.
As further preferred version, the alkene that described hydroboration refers to have the two keys in α position with described PNN part-iron complex as catalyst, with pinacol borine (HBPin) as borane reagent, at NaBHEt 3Under existing, the hydroboration of the two keys in α position occurs.
As preferred version further, described hydroboration comprises following operation:
Described PNN part-iron complex, the alkene with the two keys in α position and pinacol borine (HBPin) are added in the organic solvent, and rear adding NaHBEt stirs 3, then at room temperature stirred 10～30 minutes; Reaction system is exposed to cancellation in the air, then gained solution is carried out reduced pressure concentration; Carry out the purifying post processing.
As preferred version further, having the alkene of the two keys in α position and the mol ratio of pinacol borine is 2:1, and the mol ratio of described PNN part-iron complex and pinacol borine is 0.0025:1～0.05:1, NaHBEt 3With the mol ratio of described PNN part-iron complex be 3:1; Described organic solvent is selected from any one or a few the mixing in oxolane, toluene and the acetonitrile.
Described alkene with the two keys in α position can following general formula:
Figure BDA00002817796800031
Expression, the R1 in the general formula represents any alkyl or with the alkyl of various organo-functional groups, described functional group comprises silane, ether, acetal, sulphonic acid ester, amine, alcoxyl, internal olefin, two keys etc.; Ar in the general formula represents aryl or is with the substituent aryl such as alkyl, alkoxyl, halogen atom.
Compared with prior art, the present invention has following remarkable result:
PNN part-iron complex provided by the invention not only have 100% atom validity and good functional group compatible, and can solid form in air stable existence several weeks at least, also can stable existence in solution a couple of days;
2, PNN part-iron complex provided by the invention has good catalytic activity to the hydroboration of monoolefine, and is not only selectively good, and productive rate is high, and reaction condition is gentle;
3, the preparation method of PNN part-iron complex provided by the invention is simple, and raw material is cheap and easy to get, and is environmentally friendly, and reaction condition is gentle, and yield is higher, and post processing is simple, is easy to scale.
The specific embodiment
Below in conjunction with embodiment to the present invention do further in detail, intactly explanation.PNN part used among the embodiment is reference literature J.Am.Chem.Soc.2010, and method described in 132,16756 prepares and gets.
Embodiment 1: prepare PNN part of the present invention-iron complex A
Figure BDA00002817796800041
In glove box, with FeCl 2(0.381g, 3mmol, 1equiv) and THF (50mL) add in the 100mL Schlenk pipe, treat FeCl 2After the dissolving, the THF solution (10mL) of PNN part (1.037mg, 3.3mmol, 1.1equiv) is dropwise added mentioned solution fully, color becomes black gradually; At room temperature behind the stirring reaction 24h, drain solvent with oil pump; The solid of gained is dissolved in CH 2Cl 2(10mL), add ether (30mL), red solid is separated out again, and filters and washs with ether, gets brick-red powder (0.953g, 72%); With above-mentioned brick-red powder (30mg), be dissolved in by CH 2Cl 2(2mL) and in the mixed solvent that forms of n-hexane (2mL), then solution is placed in the glove box, after a couple of days of slowly volatilizing, have red crystals to grow, namely get PNN part of the present invention-iron complex A.
1H?NMR(CDCl 3,400MHz)δ80.92(s,1H),77.59(s,1H),53.07(s,1H),52.70(s,1H),24.94(s,2H),14.05(s,18H),9.51(s,1H),0.81(s,1H),-14.83(s,1H)；
Anal.Calcd?for?C 19H 27Cl 2FeN 2P:C,51.73;H,6.17;N,6.35.Found:C,51.56;H,6.18;N,6.20。
Embodiment 2: embodiment 1 described complex compound A is to the catalytic activity experiment of the hydroboration of different monoolefines
Figure BDA00002817796800042
2a:
Figure BDA00002817796800051
In glove box, with complex compound A (0.55mg, 0.00125mmol, 0.0025equiv), THF (2mL), 1a (84mg, 1mmol, 2equiv) and HBpin (75 μ L, 0.5mmol, 1equiv) add in the 25mL Schlenk pipe, after stirring, add NaHBEt 3(1M) (3.8 μ L, 0.00375mmol, 0.0075equiv); At room temperature behind the stirring reaction 10min, system is exposed to cancellation in the air; Gained solution is concentrated under vacuum condition, and then rapid column chromatography (the high about 5cm of silica gel, pure benzinum is as eluant, eluent) gets colourless liquid 2a (98.6mg, 93%).
1H?NMR(CDCl 3,400MHz)δ1.47-1.57(m,1H),1.39(m,2H),1.24(s,12H),1.16(m,2H),0.85(d,J=6.4Hz,6H),0.74(t,J=7.8Hz,2H)；
13C?NMR(CDCl 3,100MHz)δ83.0,42.1,27.9,24.9,22,8,21.9；
11B?NMR(CDCl 3,128MHz):δ34.0.HRMS-EI(m/z):Calcd?for[C 12H 25BO 2+],211.1984;found:211.1979。
2b:
In glove box, with complex compound A (0.55mg, 0.00125mmol, 0.0025equiv), THF (2mL), 1b (126mg, 1mmol, 2equiv) and HBpin (75 μ L, 0.5mmol, 1equiv) add in the 25mL Schlenk pipe, after stirring, add NaHBEt3 (1M) (3.8 μ L, 0.00375mmol, 0.0075equiv); At room temperature behind the stirring reaction 10min, system is exposed to cancellation in the air; Gained solution is concentrated under vacuum condition, and then rapid column chromatography (the high about 5cm of silica gel, pure benzinum is as eluant, eluent) gets colourless liquid 2b (121.2mg, 95%).
1H?NMR(CDCl 3,400MHz)δ1.31-1.39(m,2H),1.21(m,12H),1.20(s,12H),0.83(t,J=6.6Hz,3H),0.72(t,J=7.8Hz,2H)；
13C?NMR(CDCl 3,100MHz)δ80.11,29.78,29.26,26.90,26.77,26.68,22.12,21.34,20.04,11.44；
11B?NMR(CDCl 3,128MHz):δ33.9.HRMS-EI(m/z):Calcd?for[C 15H 31BO 2+],253.2453;found:2532451。
2c:
Figure BDA00002817796800061
In glove box, with complex compound A (0.55mg, 0.00125mmol, 0.0025equiv), THF (2mL), 1c (84mg, 1mmol, 2equiv) and HBpin (75 μ L, 0.5mmol, 1equiv) add in the 25mL Schlenk pipe, after stirring, add NaHBEt 3(1M) (3.8 μ L, 0.00375mmol, 0.0075equiv); At room temperature behind the stirring reaction 10min, system is exposed to cancellation in the air; Gained solution is concentrated under vacuum condition, and then rapid column chromatography (the high about 5cm of silica gel, pure benzinum is as eluant, eluent) gets colourless liquid 2c (95.8mg, 90%).
1H?NMR(CDCl 3,400MHz)δ1.37-1.41(m,2H),1.25(m,6H),1.24(s,12H),0.87(t,J=6.6Hz,3H),0.76(t,J=7.8Hz,2H)；
13C?NMR(CDCl 3,100MHz)δ83.0,32.3,31.8,24.9,24.1,22.7,14.2；
11B?NMR(CDCl 3,128MHz):δ34.0.HRMS-EI(m/z):Calcd?for[C 12H 25BO 2+],211.1984。
2d:
Figure BDA00002817796800062
In glove box, with complex compound A (4.4mg, 0.01mmol, 0.02equiv), THF (2mL), 1d (118mg, 1mmol, 2equiv) and HBpin (75 μ L, 0.5mmol, 1equiv) add in the 25mL Schlenk pipe, after stirring, add NaHBEt 3(1M) (30 μ L, 0.03mmol, 0.06equiv); At room temperature behind the stirring reaction 30min, system is exposed to cancellation in the air; With gained solution under vacuum condition in 50 ℃ concentrated, then rapid column chromatography (the high about 5cm of silica gel, pure benzinum is as eluant, eluent) must colourless liquid 2d (112.2mg, 91%).
1H?NMR(CDCl 3,400MHz)δ7.23(m,2H),7.11-7.16(m,3H),2.59(t,J=7.8Hz,2H),1.68-1.76(m,2H),1.22(s,12H),0.81(t,J=8Hz,2H)；
13C?NMR(CDCl 3,100MHz)δ142.7,128.6,128.2,125.6,83.0,38.7,26.2,24.9；
11B?NMR(CDCl 3,128MHz):δ33.9.HRMS-EI(m):Calcd?for[C 12H 23BO 2+],245.1827;found:2451829。
2e:
Figure BDA00002817796800071
In glove box, with complex compound A (4.4mg, 0.01mmol, 0.02equiv), THF (2mL), 1e (110mg, 1mmol, 2equiv) and HBpin (75 μ L, 0.5mmol, 1equiv) add in the 25mL Schlenk pipe, after stirring, add NaHBEt3 (1M) (30 μ L, 0.03mmol, 0.06equiv); At room temperature behind the stirring reaction 30min, system is exposed to cancellation in the air; With gained solution under vacuum condition in 50 ℃ concentrated, then rapid column chromatography (the high about 5cm of silica gel, pure benzinum is as eluant, eluent) must colourless liquid 2e (110.8mg, 93%).
1H?NMR(CDCl 3,400MHz)δ1.61-1.68(m,5H),1.23-1.28(m,2H),1.19(s,12H),1.03-1.16(m,4H),0.79(m,2H),0.70(t,J=8.2Hz,2H)；
13C?NMR(CDCl 3,100MHz)δ83.0,40.2,33.2,31.6,27.0,26.7,25.0；
11B?NMR(CDCl 3,128MHz):δ34.2.HRMS-EI(m):Calcd?for[C 14H 27BO 2+],237.2140;found:237.2141。
2f：
Figure BDA00002817796800072
In glove box, with complex compound A (4.4mg, 0.01mmol, 0.02equiv), THF (2mL), 1f (84mg, 1mmol, 2equiv) and HBpin (75 μ L, 0.5mmol, 1equiv) add in the 25mL Schlenk pipe, after stirring, add NaHBEt 3(1M) (30 μ L, 0.03mmol, 0.06equiv); At room temperature behind the stirring reaction 30min, system is exposed to cancellation in the air; With gained solution under vacuum condition in 50 ℃ concentrated, then rapid column chromatography (the high about 5cm of silica gel, pure benzinum is as eluant, eluent) must colourless liquid 2f (66.0mg, 62%).
1H?NMR(CDCl 3,400MHz)δ1.28(t,J=8.6Hz,2H),1.23(s,12H),0.83(s,9H),0.69(t,J=8.6Hz,2H)；
13C?NMR(CDCl 3,100MHz)δ83.1,38.0,31.0,29.1,25.0；
11B?NMR(CDCl 3,128MHz):δ33.9.HRMS-EI(m/z):Calcd?for[C 12H 25BO 2+],211.1984;found:211.1980。
2g:
Figure BDA00002817796800081
In glove box, with complex compound A (0.55mg, 0.00125mmol, 0.0025equiv), THF (2mL), 1g (114mg, 1mmol, 2equiv) and HBpin (75 μ L, 0.5mmol, 1equiv) add in the 25mL Schlenk pipe, after stirring, add NaHBEt3 (1M) (3.8 μ L, 0.00375mmol, 0.0075equiv); At room temperature behind the stirring reaction 10min, system is exposed to cancellation in the air; Gained solution is concentrated under vacuum condition, and then rapid column chromatography (the high about 5cm of silica gel, pure benzinum is as eluant, eluent) gets colourless liquid 2g (112.5mg, 93%).
1H?NMR(CDCl 3,400MHz)δ1.35-1.43(m,2H),1.20(s,12H),0.79(t,J=7.6Hz,2H),0.48(t,J=8.4Hz,2H),-0.07(s,9H)；
13C?NMR(CDCl 3,100MHz)δ83.0,25.0,20.3,18.8,-1.4；
11B?NMR(CDCl 3,128MHz):δ33.8.HRMS-EI(m/z):Calcd?for[(C 12H 27BO 2Si-CH 3)+],226.1681;found:226.1680。
2h:
In glove box, with complex compound A (2.2mg, 0.005mmol, 0.01equiv), THF (2mL), 1h (162mg, 1mmol, 2equiv) and HBpin (75 μ L, 0.5mmol, 1equiv) add in the 25mL Schlenk pipe, after stirring, add NaHBEt3 (1M) (15 μ L, 0.015mmol, 0.03equiv); At room temperature behind the stirring reaction 30min, system is exposed to cancellation in the air; Gained solution is concentrated under vacuum condition, and then (the high about 15cm of silica gel, benzinum: ethyl acetate=20:1 V/V) get colourless liquid 2h (120.4mg, 83%) as eluant, eluent to rapid column chromatography.
1H?NMR(CDCl 3,400MHz)δ7.24-7.35(m,5H),4.45(s,2H),3.46(t,J=6.6Hz,2H),1.60-1.67(m,2H),1.45-1.52(m,2H),1.23(s,12H),0.80(t,J=7.8Hz,2H)；
13C?NMR(CDCl 3,100MHz)δ138.7,128.3,127.6,127.5,83.0,72.8,70.3,32.3,24.9,20.7；
11B?NMR(CDCl 3,128MHz):δ33.9.HRMS-EI(m/z):Calcd?for[C 17H 27BO 3+],289.2090;found:289.2091。
2i:
Figure BDA00002817796800091
In glove box, with complex compound A (2.2mg, 0.005mmol, 0.01equiv), THF (2mL), 1i (142mg, 1mmol, 2equiv) and HBpin (75 μ L, 0.5mmol, 1equiv) add in the 25mL Schlenk pipe, after stirring, add NaHBEt 3(1M) (15 μ L, 0.015mmol, 0.03equiv); At room temperature behind the stirring reaction 30min, system is exposed to cancellation in the air; Gained solution is concentrated under vacuum condition, and then (the high about 15cm of silica gel, benzinum: ethyl acetate=20:1 V/V) get colourless liquid 2i (110.2mg, 82%) as eluant, eluent to rapid column chromatography.
1H?NMR(CDCl 3,400MHz)δ3.86-3.90(m,4H),1.58(t,J=7.6Hz,2H),1.34-1.39(m,4H),1.26(s,3H),1.20(s,12H),0.74(t,J=7.2Hz,2H)；
13C?NMR(CDCl 3,100MHz)δ110.2,82.9,64.6,38.9,26.8,24.8,24.2,23.7；
11B?NMR(CDCl 3,128MHz):δ33.9.HRMS-EI(m/z):Calcd?for[(C 14H 27BO 4-CH 3)+],254.1804;found:254.1800。
2j:
In glove box, with complex compound A (2.2mg, 0.005mmol, 0.01equiv), THF (2mL), 1j (254mg, 1mmol, 2equiv) and HBpin (75 μ L, 0.5mmol, 1equiv) add in the 25mL Schlenk pipe, after stirring, add NaHBEt 3(1M) (15 μ L, 0.015mmol, 0.03equiv); At room temperature behind the stirring reaction 30min, system is exposed to cancellation in the air; Gained solution is concentrated under vacuum condition, and then (the high about 15cm of silica gel, benzinum: ethyl acetate=20:1 V/V) get colourless liquid 2j (156.3mg, 82%) as eluant, eluent to rapid column chromatography.
1H?NMR(CDCl 3,400MHz)δ7.76(d,J=8.4Hz,2H),7.32(d,J=8Hz,2H),3.98(t,J=6.6Hz,2H),2.42(s,3H),1.56-1.63(m,2H),1.16-1.36(m,6H),1.21(s,12H),0.69(t,J=7.8Hz,2H)； 13C?NMR(CDCl 3,100MHz)δ144.8,133.4,130.0,128.1,83.1,70.9,31.8,28.9,25.3,25.0,23.9,21.8；
11B?NMR(CDCl 3,128MHz):δ33.9.HRMS-ESI(m/z):Calcd?for[C 19H 31BO 5S+],381.2022;found:381.2017。
2k:
Figure BDA00002817796800101
In glove box, with complex compound A (2.2mg, 0.005mmol, 0.01equiv), THF (2mL), 1k (223mg, 1mmol, 2equiv) and HBpin (75 μ L, 0.5mmol, 1equiv) add in the 25mL Schlenk pipe, after stirring, add NaHBEt 3(1M) (15 μ L, 0.015mmol, 0.03equiv); At room temperature behind the stirring reaction 30min, system is exposed to cancellation in the air; Gained solution is concentrated under vacuum condition, and then (the high about 15cm of silica gel, benzinum: ethyl acetate=20:1 V/V) get colourless liquid 2k (167.9mg, 96%) as eluant, eluent to rapid column chromatography.
1H?NMR(CDCl 3,400MHz)δ7.18-7.35(m,7H),6.66-6.77(m,3H),4.59(s,2H),3.41(t,J=8Hz,2H),1.79-1.87(m,2H),1.29(s,12H),0.84(t,J=7.6Hz,2H)；
13C?NMR(CDCl 3,100MHz)δ148.8,139.4,129.3,128.8,126.9,126.7,116.0,112.2,83.4,54.5,53.5,25.1,21.6；
11B?NMR(CDCl 3,128MHz):δ34.0.HRMS-ESI(m/z):Calcd?for[C 22H 30BNO 2+],350.2406;found:350.2405。
2l:
Figure BDA00002817796800102
In glove box, with complex compound A (11mg, 0.025mmol, 0.05equiv), THF (2mL), 1l (118mg, 1mmol, 2equiv) and HBpin (75 μ L, 0.5mmol, 1equiv) add in the 25mL Schlenk pipe, after stirring, add NaHBEt 3(1M) (75 μ L, 0.075mmol, 0.15equiv); At room temperature behind the stirring reaction 30min, system is exposed to cancellation in the air; With gained solution under vacuum condition in 50 ℃ concentrated, then rapid column chromatography (the high about 5cm of silica gel, pure benzinum is as eluant, eluent) must colourless liquid 2l (88.6mg, 72%).
1H?NMR(CDCl 3,400MHz)δ7.25-7.30(m,4H),7.14-7.18(m,1H),3.01-3.10(m,1H),1.30(d,J=6.8Hz,3H),1.19(m,2H),1.18(s,12H)；
13C?NMR(CDCl 3,100MHz)δ149.4,128.4,126.8,125.9,83.1,36.0,25.1,25.0,24.9；
11B?NMR(CDCl 3,128MHz):δ33.5.HRMS-EI(m/z):Calcd?for[C 15H 23BO 2+],245.1827;found:245.1825。
2m:
Figure BDA00002817796800111
In glove box, with complex compound A (11mg, 0.025mmol, 0.05equiv), THF (2mL), 1m (84mg, 1mmol, 2equiv) and HBpin (75 μ L, 0.5mmol, 1equiv) add in the 25mL Schlenk pipe, after stirring, add NaHBEt 3(1M) (75 μ L, 0.075mmol, 0.15equiv); At room temperature behind the stirring reaction 30min, system is exposed to cancellation in the air; With gained solution under vacuum condition in 50 ℃ concentrated, then rapid column chromatography (the high about 5cm of silica gel, pure benzinum is as eluant, eluent) must colourless liquid 2l (85.9mg, 81%).
1H?NMR(CDCl 3,400MHz)δ1.64-1.73(m,1H),1.11-1.33(m,4H),1.23(s,12H),0.88-0.89(d,J=6.4Hz,3H),0.85(t,J=7.2Hz,3H),0.78-0.82(m,1H),0.59-0.65(m,1H)；
13C?NMR(CDCl 3,100MHz)δ82.9,42.2,29.4,25.0,24.9,22.5,20.5,14.5；
11B?NMR(CDCl 3,128MHz):δ33.8.HRMS-EI(m/z):Calcd?for[C 12H 25BO 2+],211.1982;found:211.1980。
2n:
In glove box, with complex compound A (4.4mg, 0.01mmol, 0.02equiv), THF (2mL), 1n (108mg, 1mmol, 2equiv) and HBpin (75 μ L, 0.5mmol, 1equiv) add in the 25mL Schlenk pipe, after stirring, add NaHBEt 3(1M) (30 μ L, 0.03mmol, 0.06equiv); At room temperature behind the stirring reaction 30min, system is exposed to cancellation in the air; With gained solution under vacuum condition in 50 ℃ concentrated, then rapid column chromatography (the high about 5cm of silica gel, pure benzinum is as eluant, eluent) must colourless liquid 2n (112.2mg, 95%).
1H?NMR(CDCl 3,400MHz)δ5.55-5.62(m,2H),1.96-2.07(m,2H),1.53-1.71(m,2H),1.30-1.40(m,3H),1.09-1.19(m,2H),1.19(s,12H),0.74(t,J=8Hz,2H)；
13C?NMR(CDCl 3,100MHz)δ127.0,126.7,82.8,35.8,31.6,30.7,28.5,25.3,24.8；
11B?NMR(CDCl 3,128MHz):δ33.8.HRMS-EI(m/z):Calcd?for[C 14H 25BO 2+],235.1984;found:235.1987。
2o:
Figure BDA00002817796800121
In glove box, with complex compound A (11mg, 0.025mmol, 0.05equiv), THF (2mL), 1o (136mg, 1mmol, 2equiv) and HBpin (75 μ L, 0.5mmol, 1equiv) add in the 25mL Schlenk pipe, after stirring, add NaHBEt 3(1M) (75 μ L, 0.075mmol, 0.15equiv); At room temperature behind the stirring reaction 30min, system is exposed to cancellation in the air; With gained solution under vacuum condition in 50 ℃ concentrated, then (the high about 15cm of silica gel, benzinum: ethyl acetate=10:1 V/V) must colourless liquid 2o (100.2mg, 76%) as eluant, eluent for rapid column chromatography.
1H?NMR(CDCl 3,400MHz)δ5.34(t,J=1.6Hz,1H),1.85-1.98(m,3H),1.63-1.74(m,3H),1.61(s,3H),1.06-1.38(m,2H),1.22(s,12H),0.84-0.89(m,4H),0.58-0.64(m,1H)；
13C?NMR(CDCl 3,100MHz)δ134.0,121.2,83.0,40.7,34.0,33.9,31.1,29.3,28.5,26.9,26.0,25.1,24.9,23.6,19.5,19.2；
11B?NMR(CDCl 3,128MHz):δ34.3.HRMS-EI(m/z):Calcd?for[C 16H 29BO 2+],263.2297;found:263.2298。
2p:
Figure BDA00002817796800122
In glove box, with complex compound A (0.55mg, 0.00125mmol, 0.0025equiv), THF (2mL), 1p (82mg, 1mmol, 2equiv) and HBpin (75 μ L, 0.5mmol, 1equiv) add in the 25mL Schlenk pipe, after stirring, add NaHBEt 3(1M) (3.8 μ L, 0.00375mmol, 0.0075equiv); At room temperature behind the stirring reaction 10min, system is exposed to cancellation in the air; Gained solution is concentrated under vacuum condition, and then rapid column chromatography (the high about 5cm of silica gel, pure benzinum is as eluant, eluent) gets colourless liquid 2p (94.7mg, 90%).
The nuclear magnetic data of the anti conformation of 2p compound: 1H NMR (CDCl 3, 400MHz) δ 5.34-5.37 (m, 2H), 1.90-1.95 (m, 2H), 1.59 (dd, J=2.2,1Hz, 3H), 1.38-1.46 (m, 2H), 1.20 (s, 12H), 0.72 (t, J=8Hz, 2H); 13C NMR (CDCl 3, 100MHz) δ 131.4,124.9, and 82.8,35.2,24.8,24.0,18.0;
11B?NMR(CDCl 3,128MHz):δ34.0.HRMS-EI(m/z):Calcd?for[C 12H 23BO 2+],209.1827;found:209.1831。
By above-mentioned experimental result as seen: (0.25～5mol%) as catalyst to adopt PNN part-iron complex of the present invention, pinacol is as borane reagent, can make the olefine selective ground with the two keys in α position that anti-Ma Shi hydroboration occurs, the product boron alkyl acid esters that generates, all more stable to water and oxygen, can separate by rapid column chromatography.For simple chain alkene 1a-c (2equiv), just can transform fully in 10 minutes, generate 2a-c, isolated yield reaches 90～95%; 3-phenyl propylene and cyclohexyl ethene (1d, 91%) and (1e, 93%) also can obtain good yield; But for steric hindrance larger 3, the 3-neohexene, the productive rate of hydroboration product 2f is relatively low, only has 62%; And described complex compound catalyst also has preferably compatiblely with various functional groups, can make silane (1g, 87%), ether (1h, 83%), acetal (1i, 82%), sulphonic acid ester (1j, 82%), and amine (1k, 96%) higher productive rate can both be arranged; The more important thing is that for the dibasic alkene of 1,1-, can both be generated 2l and 2m by hydroboration effectively such as AMS and 2-Methyl-1-pentene, productive rate is respectively 72 and 81%; In addition, only in the end position hydroboration occurs for 4 vinyl cyclohexene 1n, intramolecular pair of key do not change, and generates product 2n, and productive rate is 95%; For (+/-) citrene, only have equally two keys of end position by hydroboration, generate 2o, productive rate is 76%; And, for Isosorbide-5-Nitrae-hexadiene 1p (trans/cis=12/1), double bond migration does not occur in the course of reaction, generate 2p, productive rate 90% (trans/cis=12/1).In sum as can be known: (0.25～5mol%) as catalyst to adopt PNN part-iron complex of the present invention, pinacol is as borane reagent, can make the alkene with the two keys in α position only hold the selective hydroboration of two keys, and catalytic activity and selective all highly significants.
Embodiment 3: embodiment 1 described complex compound A is to the catalytic activity experiment of the hydroboration of aryl ethylene
Figure BDA00002817796800131
9a:
Figure BDA00002817796800141
In glove box, with complex compound A (4.4mg, 0.01mmol, 0.02equiv), toluene (2mL), acetonitrile (5 μ L, 10equiv), 8a (104mg, 1mmol, 2equiv) and HBpin (75 μ L, 0.5mmol, 1equiv) add in the 25mL Schlenk pipe, after stirring, add NaHBEt3 (1M) (30 μ L, 0.03mmol, 0.06equiv); At room temperature behind the stirring reaction 30min, system is exposed to cancellation in the air; With gained solution under vacuum condition in 50 ℃ concentrated, then rapid column chromatography (the high about 5cm of silica gel, pure benzinum is as eluant, eluent) must colourless liquid 9a (87.3mg, 75%).
1H?NMR(CDCl 3,400MHz)δ7.20-7.27(m,4H),7.14(t,J=7Hz,1H),2.75(t,J=8.2Hz,2H),1.21(s,12H),1.14(t,J=8.2Hz,2H)；
13C?NMR(CDCl 3,100MHz)δ144.4,128.2,128.0,125.5,83.1,30.0,24.8；
11B?NMR(CDCl 3,128MHz):δ33.7.HRMS-EI(m/z):Calcd?for[C 14H 21BO 2+],231.1671;found:231.1670。
9b:
Figure BDA00002817796800142
In glove box, with complex compound A (4.4mg, 0.01mmol, 0.02equiv), toluene (2mL), acetonitrile (5 μ L, 10equiv), 8b (118mg, 1mmol, 2equiv) and HBpin (75 μ L, 0.5mmol, 1equiv) add in the 25mL Schlenk pipe, after stirring, add NaHBEt 3(1M) (30 μ L, 0.03mmol, 0.06equiv); At room temperature behind the stirring reaction 30min, system is exposed to cancellation in the air; With gained solution under vacuum condition in 50 ℃ concentrated, then rapid column chromatography (the high about 5cm of silica gel, pure benzinum is as eluant, eluent) must colourless liquid 9b (103.1mg, 84%).
1H?NMR(CDCl 3,400MHz)δ7.08(m,4H),2.70(t,J=8.4Hz,2H),2.30(s,3H),1.23(s,12H),1.12(t,J=8.4Hz,2H)；
13C?NMR(CDCl 3,100MHz)δ141.4,134.9,128.9,127.9,83.1,29.6,24.9,21.0；
11B?NMR(CDCl 3,128MHz):δ33.8.HRMS-EI(m/z):Calcd?for[C 15H 23BO 2+],245.1827;found:245.1828。
9c:
Figure BDA00002817796800151
In glove box, with complex compound A (4.4mg, 0.01mmol, 0.02equiv), toluene (2mL), acetonitrile (5 μ L, 10equiv), 8c (134mg, 1mmol, 2equiv) and HBpin (75 μ L, 0.5mmol, 1equiv) add in the 25mL Schlenk pipe, after stirring, add NaHBEt 3(1M) (30 μ L, 0.03mmol, 0.06equiv); At room temperature behind the stirring reaction 30min, system is exposed to cancellation in the air; With gained solution under vacuum condition in 50 ℃ concentrated, then (the high about 15cm of silica gel, benzinum: ethyl acetate=50:1 V/V) must colourless liquid 9c (89.5mg, 68%) as eluant, eluent for rapid column chromatography.
1H?NMR(CDCl 3,400MHz)δ7.13(d,J=8.4Hz,2H),6.80(t,J=8.4Hz,2H),3.77(s,3H),2.69(t,J=8.2Hz,2H),1.22(s,12H),1.11(t,J=8.2Hz,2H)；
13C?NMR(CDCl 3,100MHz)δ157.8,136.8,129.1,113.8,83.3,55.5,29.3,25.0；
11B?NMR(CDCl 3,128MHz):δ33.8.HRMS-EI(m/z):Calcd?for[C 15H 23BO 3+],261.1777;found:261.1781。
9d:
Figure BDA00002817796800152
In glove box, with complex compound A (4.4mg, 0.01mmol, 0.02equiv), toluene (2mL), acetonitrile (5 μ L, 10equiv), 8d (122mg, 1mmol, 2equiv) and HBpin (75 μ L, 0.5mmol, 1equiv) add in the 25mL Schlenk pipe, after stirring, add NaHBEt 3(1M) (30 μ L, 0.03mmol, 0.06equiv); At room temperature behind the stirring reaction 30min, system is exposed to cancellation in the air; With gained solution under vacuum condition in 50 ℃ concentrated, then rapid column chromatography (the high about 5cm of silica gel, pure benzinum is as eluant, eluent) must colourless liquid 9d (89.6mg, 72%).
1H?NMR(CDCl 3,400MHz)δ7.15(m,2H),6.93(m,2H),2.71(t,J=8.2Hz,2H),1.21(s,12H),1.11(t,J=8.2Hz,2H)；
13C?NMR(CDCl 3,100MHz)δ161.4(d,J=966Hz),140.2(d,J=12.4Hz),129.6(d,J=30.4Hz),115.0(d,J=83.2Hz),83.4,29.4,25.0；
19F?NMR(CDCl 3,376MHz):δ118.4. 11B?NMR(CDCl 3,128MHz):δ33.6.HRMS-EI(m/z):Calcd?for[C 14H 20BO 2F+],249.1577;found:249.1580。
To sum up experimental result as seen: adopt PNN part-iron complex of the present invention as catalyst, pinacol is as borane reagent, can make the aryl olefin with the two keys in α position only hold the selective hydroboration of two keys, and catalytic activity and selective all highly significants.
Comparative Examples
Figure BDA00002817796800161
Figure BDA00002817796800162
Reaction condition: HBPin (0.5mmol, 1equiv), 4-methyl-1-pentene 1 (1mmol, 2equiv), solvent THF (2mL), 25 ℃ of reaction temperatures.
2 productive rate is the GC productive rate, does interior mark with mesitylene; 18% dehydrogenation boronation product is observed in [c] expression simultaneously.
By above-mentioned contrast and experiment as seen: although the complex compound of the iron of the '-imine pyridinyl type part of Ritter 3 as catalyst to 1, the hydroboration of 3-diene has good activity (J.Am.Chem.Soc.2009,131,12915), but complex compound 3 at NaBHEt 3In the situation about (15mol%) existing to the catalytic effect of the hydroboration of alpha-olefin very poor (seeing route 1); When FeCl is directly used in reaction 2(5mol%) or with FeCl 2(5mol%) with 2, when 2 '-bipyridyl (5mol%) adds in the reaction as catalyst, almost there is not product (seeing route 2 and 3); In addition, when with the iron complex 4 (5mol%) of PN part that contains the bidentate type during as catalyst, as solvent, reaction is 1 hour under the room temperature with THF, has 5% anti-Ma Shi hydroboration product 2 to generate (seeing route 4); Use (terpy) FeCl 25 (5mol%) and (iPrPDI) FeCl 26 (5mol%) are as catalyst, obtain 2 (seeing route 5 and 6) with 9 and 61% yield respectively; But adopt PNN part-iron complex provided by the invention as catalyst, only needed 10 minutes just can make conversion yield reach 99%.
In sum as seen: PNN part-iron complex provided by the invention has good catalytic activity to the hydroboration of monoolefine, has the conspicuousness progress with respect to prior art.
Be necessary at last in this explanation to be: above-described embodiment only is used for technical scheme of the present invention is described in more detail; can not be interpreted as limiting the scope of the invention, some nonessential improvement that those skilled in the art's foregoing according to the present invention is made and adjustment all belong to protection scope of the present invention.

Claims (10)

1. PNN part-iron complex catalyst is characterized in that, is the compound with following general formula:
Figure FDA00002817796700011
In the general formula: R is C 1～C 30Alkyl or C 6～C 30Aryl; X is halogen atom.
2. the preparation method of PNN part claimed in claim 1-iron complex catalyst is characterized in that: be with PNN part and FeX 2Carry out complexation reaction, reaction expression is as follows:
Figure FDA00002817796700012
Described in R in the general formula and the definition of X such as the claim 1.
3. preparation method as claimed in claim 2 is characterized in that, the operation of described complexation reaction comprises the steps:
A) preparation FeX 2Tetrahydrofuran solution and the tetrahydrofuran solution of PNN part;
B) be controlled under 20～30 ℃, the tetrahydrofuran solution of PNN part is dropwise added FeX 2Tetrahydrofuran solution in;
C) drip and finish, at room temperature stirring reaction;
D) reaction finishes, and concentrated dried solvent carries out the purifying post processing.
4. preparation method as claimed in claim 3 is characterized in that: FeX 2The molar concentration of tetrahydrofuran solution be 0.01 mol/L～0.1 mol/L; The molar concentration of the tetrahydrofuran solution of PNN part is 0.1 mol/L～1.0 mol/L; PNN part and FeX 2Mol ratio be 1:1～2:1.
5. preparation method as claimed in claim 3 is characterized in that, described purifying post processing comprises the steps:
E) will concentrate the gained solid and be dissolved in the carrene, then add ether, and make and separate out solid;
F) filter, filter cake washs with ether, gets brick-red powder;
G) the brick-red powder of gained is dissolved in the mixed solvent that is formed by the 1:1 volume ratio by carrene and n-hexane, leaves standstill and make crystallization;
H) collect red crystals.
6. the application of PNN part claimed in claim 1-iron complex catalyst is characterized in that: the catalyst that is used as the hydroboration of monoolefine.
7. application as claimed in claim 6 is characterized in that: the hydroboration of described monoolefine refers to only occur the hydroboration of the two keys in α position.
8. application as claimed in claim 7 is characterized in that: the alkene that described hydroboration refers to have the two keys in α position with described PNN part-iron complex as catalyst, with pinacol borine (HBPin) as borane reagent, at NaBHEt 3Under existing, the hydroboration of the two keys in α position occurs.
9. application as claimed in claim 8 is characterized in that, described hydroboration comprises following operation:
Described PNN part-iron complex, the alkene with the two keys in α position and pinacol borine (HBPin) are added in the organic solvent, and rear adding NaHBEt stirs 3, then at room temperature stirred 10～30 minutes; Reaction system is exposed to cancellation in the air, then gained solution is carried out reduced pressure concentration; Carry out the purifying post processing.
10. application as claimed in claim 9 is characterized in that: having the alkene of the two keys in α position and the mol ratio of pinacol borine is 2:1, and the mol ratio of described PNN part-iron complex and pinacol borine is 0.0025:1～0.05:1, NaHBEt 3With the mol ratio of described PNN part-iron complex be 3:1; Described organic solvent is selected from any one or a few the mixing in oxolane, toluene and the acetonitrile.
CN2013100442479A 2013-02-04 2013-02-04 Pb(Ni1/3Nb2/3)O3 (PNN) ligand-iron complex catalyst and preparation method and application thereof Pending CN103071533A (en)

Priority Applications (3)

Application Number Priority Date Filing Date Title
CN2013100442479A CN103071533A (en) 2013-02-04 2013-02-04 Pb(Ni1/3Nb2/3)O3 (PNN) ligand-iron complex catalyst and preparation method and application thereof
CN201410007219.4A CN103962183B (en) 2013-02-04 2014-01-07 A kind of PNN ligand-metal complex Catalysts and its preparation method and application
PCT/CN2014/072159 WO2014117752A1 (en) 2013-02-04 2014-02-17 Pnn ligand-metal complex catalyst, preparation method therefor, and application thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN2013100442479A CN103071533A (en) 2013-02-04 2013-02-04 Pb(Ni1/3Nb2/3)O3 (PNN) ligand-iron complex catalyst and preparation method and application thereof

Publications (1)

Publication Number Publication Date
CN103071533A true CN103071533A (en) 2013-05-01

Family

ID=48148350

Family Applications (2)

Application Number Title Priority Date Filing Date
CN2013100442479A Pending CN103071533A (en) 2013-02-04 2013-02-04 Pb(Ni1/3Nb2/3)O3 (PNN) ligand-iron complex catalyst and preparation method and application thereof
CN201410007219.4A Active CN103962183B (en) 2013-02-04 2014-01-07 A kind of PNN ligand-metal complex Catalysts and its preparation method and application

Family Applications After (1)

Application Number Title Priority Date Filing Date
CN201410007219.4A Active CN103962183B (en) 2013-02-04 2014-01-07 A kind of PNN ligand-metal complex Catalysts and its preparation method and application

Country Status (2)

Country Link
CN (2) CN103071533A (en)
WO (1) WO2014117752A1 (en)

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103962183A (en) * 2013-02-04 2014-08-06 中国科学院上海有机化学研究所 PNN ligand-metal complex catalyst as well as preparation method and application thereof
CN104402919A (en) * 2014-10-22 2015-03-11 浙江大学 Method for synthesis of chiral pinacol boron ester compound
CN104725420A (en) * 2013-12-23 2015-06-24 中国科学院上海有机化学研究所 PNN ligand, PNN ligand iron or cobalt complex, and preparation method and application thereof
CN104804041A (en) * 2014-01-26 2015-07-29 中国科学院上海有机化学研究所 NCP ligand, and iridium complex, synthetic method, intermediate and application thereof
CN105665025A (en) * 2014-01-07 2016-06-15 中国科学院上海有机化学研究所 PNN ligand-cobalt complex catalyst and preparation method and application thereof
CN106432336A (en) * 2016-09-13 2017-02-22 中国科学院上海有机化学研究所 PNN ligand based on quinoline skeleton and iron complex, preparing method and application thereof
CN106478717A (en) * 2016-09-27 2017-03-08 苏州大学 Rare earth metal containing three tooth NNP parts is obstructed the synthesis of Lewis Acids and Bases pair and its application
CN106660029A (en) * 2014-01-08 2017-05-10 多伦多大学管理委员会 Iron (II) catalysts containing tridentate PNP ligands, their synthesis, and use thereof
CN110483560A (en) * 2019-08-06 2019-11-22 河北科技大学 A kind of the iron catalyst system and its application method of aliphatic olefin hydroboration synthesis of alkyl borate
CN110563752A (en) * 2019-08-06 2019-12-13 河北科技大学 method for synthesizing secondary or tertiary alkyl borate by iron-catalyzed Ma's selective hydroboration of olefin
CN114085242A (en) * 2021-12-08 2022-02-25 南京林业大学 Synthesis method of iron-catalyzed alkyl internal alkyne compound

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110944748B (en) * 2017-07-17 2022-10-28 美国陶氏有机硅公司 Catalysts involving hydrosilylation and dehydrosilylation and related methods
CN111943967B (en) * 2020-08-14 2023-03-28 温州大学 Method for synthesizing alkenyl borate compound

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
MXPA01004509A (en) * 1998-11-06 2002-05-06 Commw Scient Ind Res Org Hydroboronation process.
JP4179724B2 (en) * 2000-01-20 2008-11-12 独立行政法人科学技術振興機構 Method for producing cyclic polyether compound
CN103071533A (en) * 2013-02-04 2013-05-01 中国科学院上海有机化学研究所 Pb(Ni1/3Nb2/3)O3 (PNN) ligand-iron complex catalyst and preparation method and application thereof

Cited By (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2014117752A1 (en) * 2013-02-04 2014-08-07 中国科学院上海有机化学研究所 Pnn ligand-metal complex catalyst, preparation method therefor, and application thereof
CN103962183A (en) * 2013-02-04 2014-08-06 中国科学院上海有机化学研究所 PNN ligand-metal complex catalyst as well as preparation method and application thereof
CN104725420A (en) * 2013-12-23 2015-06-24 中国科学院上海有机化学研究所 PNN ligand, PNN ligand iron or cobalt complex, and preparation method and application thereof
CN105665025B (en) * 2014-01-07 2018-02-02 中国科学院上海有机化学研究所 A kind of PNN parts cobalt complex catalyst and its preparation method and application
CN105665025A (en) * 2014-01-07 2016-06-15 中国科学院上海有机化学研究所 PNN ligand-cobalt complex catalyst and preparation method and application thereof
CN106660029A (en) * 2014-01-08 2017-05-10 多伦多大学管理委员会 Iron (II) catalysts containing tridentate PNP ligands, their synthesis, and use thereof
CN104804041A (en) * 2014-01-26 2015-07-29 中国科学院上海有机化学研究所 NCP ligand, and iridium complex, synthetic method, intermediate and application thereof
CN104804041B (en) * 2014-01-26 2018-07-13 中国科学院上海有机化学研究所 NCP ligands, its iridium complex, synthetic method, intermediate and application
CN104402919A (en) * 2014-10-22 2015-03-11 浙江大学 Method for synthesis of chiral pinacol boron ester compound
CN106432336A (en) * 2016-09-13 2017-02-22 中国科学院上海有机化学研究所 PNN ligand based on quinoline skeleton and iron complex, preparing method and application thereof
CN106478717A (en) * 2016-09-27 2017-03-08 苏州大学 Rare earth metal containing three tooth NNP parts is obstructed the synthesis of Lewis Acids and Bases pair and its application
CN106478717B (en) * 2016-09-27 2018-05-08 苏州大学 Rare earth metal containing three tooth NNP ligands is obstructed the synthesis and its application of Lewis Acids and Bases pair
CN110483560A (en) * 2019-08-06 2019-11-22 河北科技大学 A kind of the iron catalyst system and its application method of aliphatic olefin hydroboration synthesis of alkyl borate
CN110563752A (en) * 2019-08-06 2019-12-13 河北科技大学 method for synthesizing secondary or tertiary alkyl borate by iron-catalyzed Ma's selective hydroboration of olefin
CN110563752B (en) * 2019-08-06 2022-04-01 河北科技大学 Method for synthesizing secondary or tertiary alkyl borate by iron-catalyzed Ma's selective hydroboration of olefin
CN114085242A (en) * 2021-12-08 2022-02-25 南京林业大学 Synthesis method of iron-catalyzed alkyl internal alkyne compound

Also Published As

Publication number Publication date
WO2014117752A1 (en) 2014-08-07
CN103962183B (en) 2016-06-29
CN103962183A (en) 2014-08-06

Similar Documents

Publication Publication Date Title
CN103071533A (en) Pb(Ni1/3Nb2/3)O3 (PNN) ligand-iron complex catalyst and preparation method and application thereof
CN108774271B (en) Chiral nitrogen phosphine tridentate ligand based on ferrocene skeleton and application thereof
Ueno et al. Copper‐Catalyzed Formal C H Carboxylation of Aromatic Compounds with Carbon Dioxide through Arylaluminum Intermediates
Marcoux et al. Nickel‐catalyzed synthesis of phosphonium salts from aryl halides and triphenylphosphine
Aydemir et al. Novel neutral phosphinite bridged dinuclear ruthenium (II) arene complexes and their catalytic use in transfer hydrogenation of aromatic ketones: X-ray structure of a new Schiff base, N3, N3′-di-2-hydroxybenzylidene-[2, 2′] bipyridinyl-3, 3′-diamine
JP6218153B2 (en) Ligand, metal complex containing the ligand, and reaction using the metal complex
Haberberger et al. Synthesis, Characterization and Catalytic Application of Iron Complexes Modified by Monodentate Phosphane Ligands
Aydemir et al. Rhodium-catalyzed transfer hydrogenation with functionalized bis (phosphino) amine ligands
JP2015508078A (en) Catalysts for hydrosilylation based on first row metals
Naghipour et al. Synthesis of a new class of unsymmetrical PCP′ pincer ligands and their palladium (II) complexes: X-ray structure determination of PdCl {C6H3-2-CH2PPh2-6-CH2PBut2}
Tamura et al. Design and synthesis of chiral 1, 10-phenanthroline ligand, and application in palladium catalyzed asymmetric 1, 4-addition reactions
Tang et al. α-Hydroxyimine palladium complexes: Synthesis, molecular structure, and their activities towards the Suzuki–Miyaura cross-coupling reaction
Wang et al. The ionic mononuclear and trinuclear Au (I)-complexes ligated by phosphine-functionalized ionic liquids: Synthesis, characterization, and catalysis to hydration of phenylacetylene
Bergin et al. Application of the Suzuki reaction to the asymmetric desymmetrisation of 1, 2-and 1, 3-disubstituted bulky cobalt metallocenes
Zhang et al. Phosphane‐Ligated Ionic Palladium Complexes: Synthesis, Characterization and Application as Efficient and Reusable Precatalysts for the Homogeneous Carbonylative Sonogashira Reaction under CuI‐Free Conditions
Aydemir et al. Synthesis and characterization of new bis (diphenylphosphino) aniline ligands and their complexes: X-ray crystal structure of palladium (II) and platinum (II) complexes, and application of palladium (II) complexes as pre-catalysts in Heck and Suzuki cross-coupling reactions
Muniyappan et al. Synthesis, structure and characterization of picolyl and benzyl linked biphenyl nickel NHC complexes and their catalytic activity in Suzuki-Miyaura cross-coupling reactions
Beck et al. Isolation and characterization of main group and late transition metal complexes using ortho metallated imine ligands
CN105665025B (en) A kind of PNN parts cobalt complex catalyst and its preparation method and application
Rodriguez-Zubiri et al. Pt-catalysed intermolecular hydroamination of non-activated olefins using a novel family of catalysts: Arbuzov-type phosphorus metal complexes
Aydemir et al. Cationic and neutral ruthenium (II) complexes containing both arene or Cp* and functionalized aminophosphines. Application to hydrogenation of aromatic ketones
Wechsler et al. Exploring the utility of a new chiral phosphoramidite P, N-ligand derived from (R)-BINOL and 7-azaindole in asymmetric catalysis
Pandiri et al. Synthesis and characterization of six-membered pincer nickelacycles and application in alkylation of benzothiazole
Blom et al. New palladium α-diimine complexes containing dendritic wedges for ethene oligomerisation
KR100915095B1 (en) β- boration of α, β-alkyne ester compound

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
WD01 Invention patent application deemed withdrawn after publication

Application publication date: 20130501

WD01 Invention patent application deemed withdrawn after publication