CN105665025A - PNN ligand-cobalt complex catalyst and preparation method and application thereof - Google Patents

PNN ligand-cobalt complex catalyst and preparation method and application thereof Download PDF

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CN105665025A
CN105665025A CN201610005350.6A CN201610005350A CN105665025A CN 105665025 A CN105665025 A CN 105665025A CN 201610005350 A CN201610005350 A CN 201610005350A CN 105665025 A CN105665025 A CN 105665025A
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aryl
pnn
hydroboration
cobalt complex
cdcl
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黄正
张雷
彭东杰
左自青
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Shanghai Institute of Organic Chemistry of CAS
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Abstract

The invention discloses a PNN ligand-cobalt complex catalyst and a preparation method and an application thereof. The catalyst is a compound represented by the following general formula defined in the specification, wherein M is cobalt, R is C1-C30 alkane or C6-C30 aryl; R1, R2, R3 R4, R5, R6 and R7 are independently selected from hydrogen atoms, halogen atoms, C1-C30 hydrocarbonyl, C1-C30 oxygen-containing groups, C1-C30 sulfur-containing groups, C1-C30 nitrogen-containing groups, C1-C30 phosphorus-containing groups, C1-C30 silicon-containing groups or other inert functional groups; X is a halogen atom or C1-C30 alkane. The preparation of the catalyst comprises the step of carrying out a coordination reaction of a PNN ligand with MX2 or Py2MX2. The PNN ligand-cobalt complex provided by the invention has excellent catalytic activity for a hydroboration reaction of monoolefine.

Description

A kind of PNN part-cobalt complex catalyst and its preparation method and application
Technical field
The present invention relates to a kind of PNN part-cobalt complex catalyst and its preparation method and application, specifically, relate to a kind of containing to cobalt complex catalyst of three flute profile PNN parts of electronics and preparation method thereof and its application in the hydroboration of monoolefine, belong to technical field of organic chemistry.
Background technology
Organic boronic and derivant thereof, frequently as intermediate, are widely used in organic synthesis, and such as, Suzuki-Miyaura reaction just can by organoboron compound C (sp3) form C-C key with halogenated hydrocarbons coupling. Organic boronic acid derivative compares the stability with uniqueness with other organometallic nucleophiles, and many borates just can separate purification and storage in atmosphere. Scientists has developed the method for multiple synthesis organic boric acid ester. The method that one of which is commonly used is that halogenated hydrocarbons is converted into organolithium reagent or Grignard reagent, the organometallic reagent generated reacts with the compound of boracic again prepares organic boric acid ester, but this method is poor due to functional group compatibility, generating again a large amount of inorganic salt in course of reaction, not significantly high synthesis is worth. Recently, Hartwig et al. has developed a kind of Rh as catalyst, alkane and B2Pin2The method that reaction directly generates organic boric acid ester, but reaction condition is relatively harsh. Not long ago Liu, Marder and Steel et al. report again a kind of relatively mild method, and they are catalyst, halogenated hydrocarbons and B with copper2Pin2Reaction generates organic boric acid ester, but this method needs excessive B2Pin2, and have substantial amounts of inorganic salt to produce.
It addition, organic boric acid ester can be prepared by Rh or Ir catalyzed alkene hydroboration. Although dialkyl group boron can with alkene energy direct addition, but dialkoxy borine is not under having catalysts conditions, and reaction is slowly. The hydroboration of metal catalytic can occur under very mild conditions, and has significantly high Atom economy, is a kind of effective synthesizing mean. Such as, Wilkinson catalyst has been widely used for the hydroboration of multiple alkene, but is often associated with multiple side reaction, the de-Hydroboration of such as alkene, hydrogenation etc. Another weak point is in aryl ethylene hydroboration process, and when particularly using pinacol borine as borane reagent, regioselectivity is poor.Secondly, reactivity is had a significant impact by the purity of Wilkinson catalyst, and it is careful especially that operation needs. Furthermore, in many reactions, for the conversion ratio obtained, it is necessary to add the catalyst of this kind of costliness of more Rh and Ir.
Owing to noble metal reserves are few, expensive, and due to environmental considerations, in the last few years, scientists attempts to substitute noble metal for organic catalytic reaction with rich reserves, cheap base metal on the earth. In 10 years of past, the complex of metal receives significant attention in homogeneous catalysis field. Recently, Ritter et al. reports the complex of the ferrum of '-imine pyridinyl part the hydroboration of 1,3-diene has preferably activity (J.Am.Chem.Soc.2009,131,12915). But containing the cobalt complex to three flute profile PNN parts of electronics and there is not yet any report so far as catalyst being applied in the hydroboration of more common monoolefine.
Summary of the invention
It is an object of the invention to provide a kind of PNN part-cobalt complex catalyst and its preparation method and application, increase a kind of cheap, environmental friendliness, the atom effectiveness of 100%, gentle reaction condition, simple separation method, good functional group compatibility for catalyst field and the hydroboration to monoolefine has the cobalt complex catalyst of excellent activity.
PNN part-cobalt complex catalyst of the present invention, is the compound with below formula:
In formula: R is C1～C30Alkyl or C6～C30Aryl; R1、R2、R3、R4、R5、R6、R7It is independently selected from hydrogen atom, halogen atom, C1-C30Alkyl, C1-C30Oxy radical, C1-C30Sulfur-containing group, C1-C30Nitrogen-containing group, C1-C30Phosphorus-containing groups, C1-C30Silicon-containing group or other safing function group, above-mentioned group is identical or different to each other, and wherein adjacent group each other in key cyclization or does not become key cyclization; X is halogen atom or C1～C30Alkyl; M is cobalt.
As a kind of preferred version, the R in formula is selected from ethyl, isopropyl, the tert-butyl group or phenyl; X in formula is selected from Cl, Br, I, methyl, phenyl, the tert-butyl group or trimethyl silicane methyl.
A kind of method preparing above-mentioned PNN part-cobalt complex catalyst, is by PNN part and MX2Or Py2MX2Carrying out complexation reaction, reaction expression is as follows:
When X is halogen atom:
When X is C1～C30Alkyl time:
As a kind of preferred version, described complexation reaction includes following operation:
A) preparation MX2Or Py2MX2Organic solution and the organic solution of PNN part;
B) control, at 20～30 DEG C, the organic solution of PNN part to be added dropwise over MX2Or Py2MX2Organic solution in;
C) drip finish, at room temperature stirring reaction;
D) reaction terminates, and is purified post processing.
As it is preferred that scheme, described organic solution is tetrahydrofuran solution, diethyl ether solution, tertbutyl ether solution, hexane solution, pentane solution or toluene solution.
As it is preferred that scheme, MX2Or Py2MX2The molar concentration of organic solution be 0.01 mol/L～0.1 mol/L; The molar concentration of the organic solution of PNN part is 0.1 mol/L～1.0 mol/L; PNN part and MX2Or Py2MX2Mol ratio be 1:1～2:1.
The application of a kind of described PNN part-cobalt complex catalyst, is used as the catalyst of the hydroboration of monoolefine.
As a kind of preferred version, the hydroboration of described monoolefine refers to the hydroboration that α position double bond only occurs.
As it is preferred that scheme, described hydroboration refers to that the alkene with α position double bond is using described PNN part-cobalt complex as catalyst, using pinacol borine (HBPin) as borane reagent, at NaHBEt3Under existence, there is the hydroboration of α position double bond.
As further preferred version, described hydroboration includes following operation:
1. make PNN part-cobalt complex, there is the alkene of α position double bond, pinacol borine (HBPin) and NaHBEt3At room temperature stirring reaction 10～30 minutes;
2. reaction system is exposed cancellation in atmosphere, is then purified post processing.
The condition of above-mentioned hydroboration is preferably:
The mol ratio of the alkene and pinacol borine with α position double bond is 1:1, and the mol ratio of described PNN part-cobalt complex and pinacol borine is 0.00005:1～0.01:1, NaHBEt3It is 2:1 with the mol ratio of described PNN part-cobalt complex; Described hydroboration carries out or carries out in oxolane, toluene, normal hexane or ether under solvent-free.
The described alkene with α position double bond can below formula:Represent, the R in formula8Representing any alkyl or the alkyl with various organo-functional groups, described functional group includes silane, ether, ketal, amine, amide, ester, ketone etc.; Ar in formula represents aryl or the aryl with substituent groups such as alkyl, alkoxyl, ester group, halogen atoms.
One prominent effect of the present invention, is apply PNN part-cobalt complex catalyst of the present invention to carry out monoolefine hydroboration gained hydroboration product and need not separate, it is possible to directly and chlorinated aromatic hydrocarbons realize coupling reaction.
Described coupling reaction refers to chlorinated aromatic hydrocarbons compounds and above-mentioned hydroboration product, with Pd (OAc)2With Ruphos as catalyst, realize cross-coupling reaction using potassium tert-butoxide as alkali; Including following operation:
In atmosphere, by Pd (OAc)2,KOtBu and Ruphos part adds in tube sealing, substitutes argon three times, and the hydroboration product then toluene, water, chlorinated aromatic hydrocarbons and above-mentioned hydroboration directly obtained adds in tube sealing by syringe, then stirs 24h at 80 DEG C; Reactant liquor kieselguhr is filtered, and washs by ethyl acetate, be spin-dried for solvent and obtain crude product; By further for crude product column chromatography for separation, obtain coupled product.
Preferably, the mol ratio of described hydroboration product and chlorinated aromatic hydrocarbons is 1:1, Pd (OAc)2With described hydroboration product molar than for 0.02:1, Ruphos and described hydroboration product molar than for 0.04:1; KOtBu and described hydroboration product molar are than for 3:1.
Compared with prior art, the present invention also has following remarkable result:
1, the preparation method of PNN part-cobalt complex provided by the invention is simple, and raw material is cheap and easy to get, environmentally friendly, and reaction condition is gentle, and yield is higher, and post processing is simple, it is easy to scale.
2, the hydroboration of monoolefine is had the atom effectiveness of 100% and good functional group compatibility by PNN part-cobalt complex provided by the invention;
3, the hydroboration of monoolefine is had excellent catalysis activity by PNN part-cobalt complex provided by the invention, and not only selectivity is good, and productivity is high, and reaction condition is gentle.
Detailed description of the invention
The present invention is made further in detail below in conjunction with embodiment, intactly illustrates. PNN part used in embodiment is that method described in reference literature J.Am.Chem.Soc.2010,132,16756 is prepared and obtained.
Embodiment 1: preparation PNN part-cobalt complex
(tBu-PNN)CoCl2(complex A):
In glove box, by CoCl2(260mg, 2.0mmol, 1.0equiv) and THF (50mL) add in 100mLschlenk pipe, more slowly willtThe THF solution (10mL) of Bu-PNN part (628mg, 2.0mmol, 1.0equiv) is added dropwise over above-mentioned solution, the blackening gradually of reactant liquor color. After reaction at room temperature stirring 24h, with oil pump concentration of reaction solution to 10mL, add Et2O, treats that solid precipitates out, and filters and with washed with diethylether, drains solvent and obtain purple powder (826mg, 93%). Then by above-mentioned powder (50mg), it is dissolved in CH2Cl2(3mL), 1mLCH is added on solution upper strata2Cl2With the mixed solvent (1:1) of normal hexane as cushion, mixed solvent upper strata adds a large amount of normal hexane, stands a couple of days, treats that normal hexane is slowly diffused into the CH of complex2Cl2In solution, obtain atropurpureus crystal, for single crystal diffraction.
1HNMR(CDCl3, 400MHz) and δ 123.37,86.98,67.83,64.98,43.57,40.69,25.36 ,-2.97 ,-4.70; Anal.CalcdforC19H27Cl2CoN2P:C, 51.37; H, 6.13; N, 6.31.Found:C, 51.45; H, 6.19; N, 6.32.
(iPr-PNN)CoCl2(complex B):
In glove box, by CoCl2(260mg, 2.0mmol, 1.0equiv) and THF (50mL) add in 100mLSchlenk pipe, more slowly williThe THF solution (10mL) of Pr-PNN part (573mg, 2.0mmol, 1.0equiv) is added dropwise over above-mentioned solution, the blackening gradually of reactant liquor color. After reaction at room temperature stirring 24h, with oil pump concentration of reaction solution to 10mL, add Et2O, treats that solid precipitates out, and filters and with washed with diethylether, drains solvent and obtain brown ceramic powder (622mg, 75%). Then by above-mentioned powder (50mg), it is dissolved in CH2Cl2(3mL), 1mLCH is added on solution upper strata2Cl2With the mixed solvent (1:1) of normal hexane as cushion, mixed solvent upper strata adds a large amount of normal hexane, stands a couple of days, treats that normal hexane is slowly diffused into the CH of complex2Cl2In solution, obtain black crystals, for single crystal diffraction.
1HNMR(CDCl3,400MHz)δ120.09,89.45,73.37,62.84,54.67,53.99,34.30,18.31,-6.15,-13.74,-14.16.Anal.CalcdforC17H23Cl2CoN2P+H2O:C, 47.02; H, 5.80; N, 6.45.Found:C, 46.96; H, 5.59; N, 6.41.
(iPr-PNN) CoCH2SiCH3 (complex D):
In glove box, by Py2Co (CH2SiCH3) 2 (392mg, 1.0mmol, 1.0equiv) add in 25mLSchlenk pipe with pentane (10mL), again slowly by iPr-PNN part (286mg, 1.0mmol, 1.0equiv) pentane solution (5mL) be added dropwise over above-mentioned solution. Reaction is stirring 1 hour at room temperature, filters to obtain dark solution with kieselguhr, and solvent drained by oil pump, adds 5ml pentane, the black solid powder (263mg, 51%) of recrystallization at being placed in-35 DEG C. 1HNMR (400MHz, C6D6) δ=14.19 (s, 1H), 10.75 (s, 1H), 9.77 (s, 1H), 8.87 (t, J=6.8Hz, 1H), 7.47 (d, J=8.4Hz, 1H), 7.37 (d, J=6.2Hz, 1H), 5.60 (d, J=8.0Hz, 1H), 4.54 (d, J=9.5Hz, 2H), 3.11 2.82 (m, 2H), 1.25 (dd, J=12.7Hz, 6.9Hz, 6H), 1.14 (dd, J=12.7Hz, 6.9Hz, 6H) ,-4.57 (s, 2H) ,-11.87 (s, 9H).
Embodiment 2: the catalysis activity experiment to the hydroboration of different monoolefines of the complex B described in embodiment 1
Hydroboration process for alkene 1a: first in glove box, by complex B (2.1mg), THF (20mL) and NaBEt3H (1M) (10uL) adds the catalyst solution obtaining purple in 50ml conical flask; Then alkene 1a (63mg, 0.5mmol, 1equiv) and HBpin (75uL, 0.5mmol, 1equiv) is added in the reaction bottle of 8mL, then take in the catalyst solution 1mL above-mentioned reaction bottle of addition configured;After reaction at room temperature stirring 15min, it is exposed in air cancellation; Then rotation is evaporated off solvent, and rapid column chromatography (the high about 5cm of silica gel, the mixture of petroleum ether and ethyl acetate makes eluant) obtains colourless liquid 3a. 3b～3n, 4b～4m preparation method with the preparation method of 3a.
4,4,5,5-tetramethyl-2-nonyl-1,3,2-dioxaborolane (3a):
Colourless liquid (121.0mg, 95%);1HNMR(400MHz,CDCl3) δ=1.35-1.43 (m, 2H, CH3CH2),1.34-1.16(m,12H,CH2),1.24(s,12H,OC(CH3)2), 0.87 (t, J=6.9Hz, 3H, CH3CH2), 0.79-0.73 (t, J=7.8Hz, 2H, BCH2).13CNMR(101MHz,CDCl3)δ82.9(OC(CH3)2),32.5(CH2),32.0(CH2),29.7(CH2),29.5(CH2),29.5(CH2),24.9(C(CH3)2),24.1(CH2),22.8(CH2),14.2(CH3).
4,4,5,5-tetramethyl-2-(4-methylpentyl)-1,3,2-dioxaborolane (3b):
Colourless liquid (101.0mg, 95%);1HNMR(400MHz,CDCl3) δ=1.49 (m, 1H, CH (CH3)2),1.41-1.31(m,2H,CH2CH(CH3)2),1.20(s,12H,OC(CH3)2),1.16-1.09(m,2H,BCH2CH2), 0.82 (d, J=6.6Hz, 6H, CH (CH3)2), 0.70 (t, J=7.8Hz, 2H, BCH2).13CNMR(101MHz,CDCl3)δ82.7(OC(CH3)2),41.8(CH2CH(CH3)2),27.7(CH(CH3)2),24.7(C(CH3)2),22.5(CH2CH(CH3)2),21.7(BCH2CH2).
Trimethyl (3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) propyl) silane (3c):
Colourless liquid (105.0mg, 87%);1HNMR(400MHz,CDCl3) δ=1.43-1.34 (m, 2H, CH2CH2B),1.19(s,12H,OC(CH3)2), 0.78 (t, J=7.6Hz, 2H, BCH2),0.51-0.44(m,2H,SiCH2),-0.09(s,9H,Si(CH3)3).13CNMR(101MHz,CDCl3)δ82.8(OC(CH3)2),24.9(C(CH3)2),20.2(CH2),18.7(CH2),-1.5(Si(CH3)3).
4,4,5,5-tetramethyl-2-(3-phenylpropyl)-1,3,2-dioxaborolane (3d):
Colourless liquid (106.0mg, 86%);1HNMR(400MHz,CDCl3) δ=7.28-7.21 (m, 2H, aryl-H), 7.19-7.11 (m, 3H, aryl-H), 2.60 (t, J=7.8Hz, 2H, PhCH2),1.69-1.77(m,2H,CH2CH2B),1.22(s,12H,OC(CH3)2), 0.82 (t, J=8.0Hz, 2H, CH2B).13CNMR(101MHz,CDCl3)δ142.7 (aryl-C),128.6(aryl-C),128.2(aryl-C),125.6(aryl-C),83.0(OC(CH3)2),38.6(PhCH2),26.2(CH2CH2B),24.9(C(CH3)2).
2-(2-cyclohexylethyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (3e):
Colourless liquid (115.0mg, 97%).1HNMR(400MHz,CDCl3) δ=1.61-1.71 (m, 4H, cyclohexyl-H), 1.30-1.03 (m, 7H, cyclohexyl-H), 1.21 (s, 12H, OC (CH3)2),0.77-0.85(m,2H,CH2CH2B), 0.72 (t, J=8.2Hz, 2H, CH2B).13CNMR(101MHz,CDCl3)δ82.9(OC(CH3)2),40.1(CH),33.1(CH2),31.5(CH2),26.9(CH2),26.5(CH2),24.9(C(CH3)2).
2-(2-(cyclohex-3-en-1-yl) ethyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (3f):
Colourless liquid (113.0mg, 96%);1HNMR(400MHz,CDCl3) δ=5.56-5.63 (m, 2H, CH=CH), 2.12-1.93 (m, 3H), 1.77-1.65 (m, 1H), 1.62-1.51 (m, 1H), 1.46-1.29 (m, 3H), 1.21 (s, 12H, OC (CH3)2), 1.20-1.08 (m, 1H), 0.75 (t, J=8.2Hz, 2H, CH2B).13CNMR(101MHz,CDCl3) δ 126.9 (CH=CH), 126.6 (CH=CH), 82.8 (OC (CH3)2),35.7,31.5,30.6,28.5,25.3,24.7(C(CH3)2).
2-(6-chlorohexyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (3g):Colourless liquid (118.0mg, 96%);1HNMR(400MHz,CDCl3) δ=3.48 (t, J=6.8Hz, 2H, ClCH2),1.78-1.68(m,2H,CH2),1.35-1.43(m,4H,CH2),1.32-1.25(m,2H,CH2),1.21(s,12H,OC(CH3)2), 0.74 (t, J=7.6Hz, 2H, CH2B).13CNMR(101MHz,CDCl3)δ83.0(OC(CH3)2),45.2(ClCH2),32.6(CH2),31.6(CH2),26.7(CH2),24.9(C(CH3)2),23.9(CH2).HRMS-EI(m/z):Calcdfor[C12H24BO2Cl+], 245.1594; Found:245.1598.
N, N-diethyl-3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) propan-1-amine (3h):
Colourless liquid (105.0mg, 87%);1HNMR(400MHz,CDCl3) δ=2.45 (q, J=7.2Hz, 4H, NCH2CH3),2.37-2.29(m,2H,NCH2CH2),1.54-1.42(m,2H,NCH2CH2),1.17(s, 12H,OC(CH3)2), 0.94 (t, J=7.2Hz, 6H, NCH2CH3), 0.65 (t, J=7.7Hz, 2H, CH2B).13CNMR(101MHz,CDCl3)δ83.0(OC(CH3)2),54.7(NCH2CH2),46.7(NCH2CH3),24.8(C(CH3)2),20.6(NCH2CH2),11.4(NCH2CH3).HRMS-ESI(m/z):Calcdfor[(C13H29BNO2+ H)+], 241.2322; Found:241.2325.
N, N-dimethyl-5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) pentanamide (3i):
Colourless liquid (105.0mg, 87%);1HNMR(400MHz,CDCl3) δ=2.95 (s, 3H, NCH3),2.89(s,3H,NCH3), 2.27 (t, J=7.7Hz, 2H, COCH2),1.56-1.64(m,2H,COCH2CH2),1.38-1.46(m,2H,BCH2CH2),1.20(s,12H,OC(CH3)2), 0.77 (t, J=7.8Hz, 2H, CH2B).13CNMR(101MHz,CDCl3)δ173.2(CO),82.9(OC(CH3)2),37.2(NCH3),35.3(NCH3),33.3(COCH2),27.7(COCH2CH2),24.8(C(CH3)2),23.9(BCH2CH2).HRMS-ESI(m/z):Calcdfor[(C13H27BNO3+ H)+], 255.2115; Found:255.2111.
Tert-butyldiphenyl ((6-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) hexyl) oxy) silane (3j):
Colourless liquid (224.0mg, 96%);1HNMR(400MHz,CDCl3) δ=7.77-7.71 (m, 4H, aryl-H), 7.49-7.38 (m, 6H, aryl-H), 3.72 (t, J=6.5Hz, 2H, OCH2),1.66-1.59(m,2H,OCH2CH2),1.52-1.32(m,6H,CH2),1.29(s,12H,OC(CH3)2),1.11(s,9H,SiC(CH3)3), 0.83 (t, J=7.7Hz, 2H, CH2B).13CNMR(101MHz,CDCl3)δ135.6(aryl-C),134.2(aryl-C),129.5(aryl-C),127.7(aryl-C),82.9(OC(CH3)2),64.1(OCH2),32.7,32.3,27.0(C(CH3)3),25.7,24.9(C(CH3)2),24.1,19.3.HRMS-ESI(m/z):Calcdfor[(C28H47BNO3Si+NH4)+], 484.3418; Found:484.3416.
2-(3-ethoxypropyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (3k):Colourless liquid (77.0mg, 72%);1HNMR(400MHz,CDCl3) δ=3.44 (q, J=7.0Hz, 2H, OCH2CH3), 3.35 (t, J=6.8Hz, 2H, OCH2CH2),1.73-1.60(m,2H,OCH2CH2),1.21(s,12H,OC(CH3)2), 1.16 (t, J=7.0Hz, 3H, OCH2CH3), 0.77 (t, J=7.8Hz, 2H, CH2B).13CNMR(101MHz,CDCl3)δ83.0(OC(CH3)2),72.5(OCH2CH2),66.0(OCH2CH3),24.9(C(CH3)2),24.3(OCH2CH2),15.4(OCH2CH3).HRMS-EI(m/z):Calcdfor[(C11H23BO3-CH3)+], 198.1542; Found:198.1538.
2-(3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) propyl) cyclohexanone (3l):
Colourless liquid (122.0mg, 92%);1HNMR(400MHz,CDCl3) δ=2.34-2.26 (m, 1H), 2.15-2.24 (m, 2H), 2.08-1.99 (m, 1H), 1.98-1.89 (m, 1H), 1.80-1.68 (m, 2H), 1.64-1.53 (m, 2H), 1.38-1.25 (m, 3H), 1.18-1.10 (m, 1H), 1.16 (s, 12H, OC (CH3)2),0.69(m,2H,CH2B).13CNMR(101MHz,CDCl3)δ213.41(CO),82.79(OC(CH3)2),50.47(COCH),41.83(COCH2),33.7,32.0,28.0,24.7(C(CH3)2),24.7,21.5.HRMS-EI(m/z):Calcdfor[C15H27BO3+], 265.2090; Found:265.2094.
7-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) heptan-3-one (3m):Colourless liquid (91.0mg, 76%);1HNMR(400MHz,CDCl3) δ=2.35-2.26 (m, 4H, CH2COCH2),1.43-1.52(m,2H,COCH2CH2),1.34-1.26(m,2H,CH2CH2B),1.13(s,12H,OC(CH3)2), 0.93 (t, J=7.3Hz, 3H, CH3CH2), 0.67 (t, J=7.8Hz, 2H, CH2B).13CNMR(101MHz,CDCl3)δ211.6(CO),82.8(OC(CH3)2),42.2(COCH2CH2),35.6(COCH2CH3),26.4(COCH2CH2),24.7(C(CH3)2),23.6(CH2CH2B),7.7(CH3CH2).HRMS-EI(m/z):Calcdfor[C13H25BO3+], 239.1933; Found:239.1934.
4,4,5,5-tetramethyl-2-(5-methylhex-5-en-1-yl)-1,3,2-dioxaborolane (3n):
Colourless liquid (105.0mg, 94%);1HNMR(400MHz,CDCl3) δ=4.68-4.61 (m, 2H, C=CH2), 1.98 (t, J=6.8Hz, 2H ,=CCH2), 1.68 (s, 3H ,=CCH3),1.35-1.45(m,4H,CH2),1.22(s,12H,OC(CH3)2), 0.77 (t, J=7.2Hz, 2H, BCH2).13CNMR(101MHz,CDCl3) δ 146.3 (C=CH2), 109.6 (C=CH2),83.0(OC(CH3)2), 37.8 (=CCH2),30.5,24.9(C(CH3)2),23.8,22.5.HRMS-EI(m/z):Calcdfor[C13H25BO2+], 223.1984; Found:223.1987.
4,4,5,5-tetramethyl-2-phenethyl-1,3,2-dioxaborolane (4a):
Colourless liquid (106.0mg, 91%);1HNMR(400MHz,CDCl3) δ=7.34-7.24 (m, 4H, aryl-H), 7.23-7.16 (m, 1H, aryl-H), 2.80 (t, J=8.0Hz, 2H, PhCH2),1.26(s,12H,C(CH3)2), 1.20 (t, J=8.0Hz, 2H, BCH2).13CNMR(101MHz,CDCl3)δ144.5(aryl-C),128.3(aryl-C),128.1(aryl-C),125.6(aryl-C),83.2(OC(CH3)2),30.1(PhCH2),24.9(C(CH3)2).
4,4,5,5-tetramethyl-2-(4-methylphenethyl)-1,3,2-dioxaborolane (4b):Colourless liquid (114.0mg, 93%);1HNMR(400MHz,CDCl3) δ=7.13 (m, 4H, aryl-H), 2.76 (t, J=8.2Hz, 2H, PhCH2),2.34(s,3H,PhCH3),1.27(s,12H,C(CH3)2), 1.17 (t, J=8.2Hz, 2H, BCH2).13CNMR(101MHz,CDCl3)δ141.4(aryl-C),134.9(aryl-C),128.9(aryl-C),127.9(aryl-C),83.1(OC(CH3)2),29.6(PhCH2),24.9(C(CH3)2),21.05(PhCH3).
4,4,5,5-tetramethyl-2-(3-methylphenethyl)-1,3,2-dioxaborolane (4c):Colourless liquid (119.0mg, 97%);1HNMR(400MHz,CDCl3) δ=7.19 (t, J=7.5Hz, 1H, aryl-H), 7.13-6.98 (m, 3H, aryl-H), 2.76 (t, J=8.1Hz, 2H, PhCH2),2.36(s,3H,PhCH3),1.26(s,12H,C(CH3)2), 1.18 (t, J=8.1Hz, 2H, BCH2).13CNMR(101MHz,CDCl3)δ144.3(aryl-C),137.6(aryl-C),128.8(aryl-C),128.1(aryl-C),126.2(aryl-C),125.0(aryl-C),83.0(OC(CH3)2),29.9(PhCH2),24.8(C(CH3)2),21.4(PhCH3).HRMS-EI(m/z):Calcdfor[C15H23BO2+],245.1827,found:245.1830.
2-(4-methoxyphenethyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (4d):
Colourless liquid (126.0mg, 96%);1HNMR(400MHz,CDCl3) δ=7.14 (d, J=8.6Hz, 2H, aryl-H), 6.81 (d, J=8.6Hz, 2H, aryl-H), 3.77 (s, 3H, OCH3), 2.70 (t, J=8.0Hz, 2H, PhCH2),1.22(s,12H,C(CH3)2), 1.12 (t, J=8.2Hz, 2H, BCH2).13CNMR(101MHz,CDCl3)δ157.6(aryl-C),136.6(aryl-C),128.9(aryl-C),113.6(aryl-C),83.1(OC(CH3)2),55.3(OCH3),29.1(PhCH2),24.9(C(CH3)2).
2-(4-(tert-butoxy) phenethyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (4e):
Colourless liquid (142.0mg, 93%);1HNMR(400MHz,CDCl3) δ=7.09 (d, J=8.3Hz, 2H, aryl-H), 6.87 (d, J=8.3Hz, 2H, aryl-H), 2.71 (t, J=8.0Hz, 2H, PhCH2),1.31(s,9H,PhOC(CH3)3),1.19(s,12H,C(CH3)2), 1.13 (t, J=8.0Hz, 2H, BCH2).13CNMR(101MHz,CDCl3)δ153.1(aryl-C),139.4(aryl-C),128.4(aryl-C),124.2(aryl-C),83.2(OC(CH3)2),78.1(PhOC(CH3)2),29.4(PhCH2),28.9(PhOC(CH3)3),24.9(C(CH3)2).HRMS-EI(m/z):Calcdfor[C18H29BO3+], 303.2246;Found:303.2249.
2-(4-fluorophenethyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (4f):Colourless liquid (121.0mg, 97%);1HNMR(400MHz,CDCl3) δ=7.19-7.12 (m, 2H, aryl-H), 6.96-6.89 (m, 2H, aryl-H), 2.71 (t, J=8.2Hz, 2H, PhCH2),1.20(s,12H,C(CH3)2), 1.11 (t, J=8.0Hz, 2H, BCH2).13CNMR(101MHz,CDCl3) δ 161.2 (d, J=242.7Hz, aryl-C), 140.0 (d, J=3.2Hz, aryl-C), 129.4 (d, J=7.7Hz, aryl-C), (114.9 d, J=21.0Hz, aryl-C), 83.2 (OC (CH3)2),29.3(PhCH2),24.9(C(CH3)2).19FNMR(376MHz,CDCl3)δ-118.4.
2-(3-fluorophenethyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (4g):
Colourless liquid (111.0mg, 89%);1HNMR(400MHz,CDCl3) δ=7.15-7.22 (m, 1H, aryl-H), 6.97 (d, J=7.6Hz, 1H, aryl-H), 6.90-6.94 (m, 1H, aryl-H), 6.80-6.86 (m, 1H, aryl-H), 2.74 (t, J=8.1Hz, 2H, PhCH2),1.21(s,13H,C(CH3)2), 1.13 (t, J=8.2Hz, 2H, BCH2).13CNMR(101MHz,CDCl3) δ 162.8 (d, J=244.7Hz, aryl-C), 147.0 (d, J=7.1Hz, aryl-C), 129.5 (d, J=8.3Hz, aryl-C), 123.6 (d, J=2.7Hz, aryl-C), 114.8 (d, J=20.8Hz, aryl-C), 112.3 (d, J=21.0Hz, aryl-C), 83.1 (OC (CH3)2), 29.7 (d, J=1.6Hz, PhCH2),24.7(C(CH3)2).19FNMR(376MHz,CDCl3)δ-114.2.HRMS-EI(m/z):Calcdfor[C14H20BO2F+], 249.1577; Found:249.1576.
2-(4-chlorophenethyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (4h):Colourless liquid (120.0mg, 90%);1HNMR(400MHz,CDCl3) δ=7.21 (d, J=8.4Hz, 2H, aryl-H), 7.13 (d, J=8.4Hz, 2H, aryl-H), 2.71 (t, J=8.2Hz, 2H, PhCH2),1.21(s,12H,C(CH3)2), 1.11 (t, J=8.0Hz, 2H, BCH2).13CNMR(101MHz,CDCl3)δ142.9(aryl-C),131.3(aryl-C),129.5(aryl-C),128.3(aryl-C),83.3(OC(CH3)2),29.4(PhCH2),24.9(C(CH3)2).
2-(4-bromophenethyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (4i):Colourless liquid (143.0mg, 92%);1HNMR(400MHz,CDCl3) δ=7.35 (d, J=8.4Hz, 2H, aryl-H), 7.07 (d, J=8.5Hz, 2H, aryl-H), 2.69 (t, J=8.2Hz, 2H, PhCH2),1.20(s,12H,C(CH3)2), 1.10 (t, J=8.0Hz, 2H, BCH2).13CNMR(101MHz,CDCl3)δ143.3(aryl-C),131.1(aryl-C),129.8(aryl-C),119.1(aryl-C),83.1(OC(CH3)2),29.4(PhCH2),24.8(C(CH3)2).
4-(2-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) ethyl) phenylacetate (4j):
Colourless liquid (116.0mg, 80%);1HNMR(400MHz,CDCl3) δ=7.20 (d, J=8.3Hz, 2H, aryl-H), 6.95 (d, J=8.4Hz, 2H, aryl-H), 2.73 (t, J=8.0Hz, 2H, PhCH2),2.25(s,3H,CH3CO),1.20(s,12H,C(CH3)2), 1.12 (t, J=8.2Hz, 2H, BCH2).13CNMR(101MHz,CDCl3)δ169.7(CO),148.5(aryl-C),141.9(aryl-C),128.9(aryl-C),121.2(aryl-C),83.1(OC(CH3)2),29.4(PhCH2),24.8(C(CH3)2),21.1(COCH3)).HRMS-ESI(m/z):Calcdfor[(C16H23BO4+NH4)+], 307.2064; Found:307.2067.
2-(2,5-dimethylphenethyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (4k):Colourless liquid (130.0mg, 93%);1HNMR(400MHz,CDCl3) δ=7.08-7.01 (m, 2H, aryl-H), 6.93 (d, J=7.6Hz, 1H, aryl-H), 2.74 (t, J=8.0Hz, 2H, PhCH2),2.33(s,3H,PhCH3),2.32(s,3H,PhCH3),1.28(s,12H,C(CH3)2), 1.14 (t, J=8.2Hz, 2H, BCH2).13CNMR(101MHz,CDCl3)δ142.4(aryl-C),135.1(aryl-C),132.6(aryl-C),130.0(aryl-C),129.1(aryl-C),126.3(aryl-C),83.1(OC(CH3)2),27.3(PhCH2),24.9(C(CH3)2),21.1(PhCH3),18.9(PhCH3).HRMS-EI(m/z):Calcdfor[C16H25BO2+], 259.1984; Found:259.1986.
4,4,5,5-tetramethyl-2-(2-(naphthalen-2-yl) ethyl)-1,3,2-dioxaborolane (4l):
Colourless liquid (131.0mg, 93%);1HNMR(400MHz,CDCl3) δ=7.83-7.74 (m, 3H, aryl-H), 7.67 (s, 1H, aryl-H), 7.48-7.38 (m, 3H, aryl-H), 2.95 (t, J=7.9Hz, 2H, PhCH2), 1.28 (t, J=8.0Hz, 2H, BCH2),1.24(s,12H,C(CH3)2).13CNMR(101MHz,CDCl3)δ142.1(aryl-C),133.7(aryl-C),132.0(aryl-C),127.8(aryl-C),127.7(aryl-C),127.5(aryl-C),127.4(aryl-C),125.8(aryl-C),125.8(aryl-C),125.0(aryl-C),83.3(OC(CH3)2),30.3(PhCH2),24.9(C(CH3)2).
9-(2-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) ethyl)-9H-carbazole (4m):White solid (147.0mg, 92%);1HNMR(400MHz,CDCl3) δ=8.12-8.16 (m, 2H, aryl-H), 7.47-7.55 (m, 4H, aryl-H), 7.30-7.23 (m, 2H, aryl-H), 4.50 (t, J=8.0Hz, 2H, NCH2), 1.48 (t, J=8.0Hz, 2H, BCH2),1.24(s,12H,C(CH3)2).13CNMR(101MHz,CDCl3)δ140.0(aryl-C),125.5(aryl-C),123.0(aryl-C),120.3(aryl-C),118.7(aryl-C),109.1(aryl-C),83.6(OC(CH3)2),38.8(NCH2),24.9(C(CH3)2).
Embodiment 3: the alkene hydroboration carried out under condition of no solvent
In glove box, by alkene 2a (5.2g, 50mmol) and HBpin (6.4g, 50mmol, 1equiv), complex B (1.0mg) and NaBEt3H (1M) (5uL) adds in the reaction bottle of 8mL.After reaction at room temperature stirring 1h, it is exposed in air cancellation. Rapid column chromatography (the high about 5cm of silica gel, the mixture of petroleum ether and ethyl acetate makes eluant) obtains colourless liquid 4a (m=11.5g, productivity 99%).
4,4,5,5-tetramethyl-2-phenethyl-1,3,2-dioxaborolane (4a):
Colourless liquid (106.0mg, 91%);1HNMR(400MHz,CDCl3) δ=7.34-7.24 (m, 4H, aryl-H), 7.23-7.16 (m, 1H, aryl-H), 2.80 (t, J=8.0Hz, 2H, PhCH2),1.26(s,12H,C(CH3)2), 1.20 (t, J=8.0Hz, 2H, BCH2).13CNMR(101MHz,CDCl3)δ144.5(aryl-C),128.3(aryl-C),128.1(aryl-C),125.6(aryl-C),83.2(OC(CH3)2),30.1(PhCH2),24.9(C(CH3)2).
Embodiment 4: with the conjugation of embodiment 2 gained borate Yu chlorinated aromatic hydrocarbons compound
In atmosphere, by Pd (OAc)2(2.2mg,0.01mmol),KOtBu (168.0mg, 1.5mmol) add in 10mL tube sealing with Ruphos part (9.3mg, 0.02mmol), substitute argon three times, then by toluene (1.5mL), water (0.15mL), chlorobenzene (56.0mg, 0.50mmol), with the borate 4f (125.1mg that directly obtains of reaction, 0.50mmol, 1.0equiv) add in tube sealing by syringe, 24h is stirred in reaction at 80 DEG C. Then reactant liquor kieselguhr is filtered, and wash by ethyl acetate (5 × 5mL), be spin-dried for solvent and obtain crude product. Further for crude product column chromatography for separation is obtained the preparation method preparation method with 5a of white solid 5a (85.8mg, 86%) .5b～5f.
1-fluoro-4-phenethylbenzene (5a):
1HNMR(400MHz,CDCl3) δ=7.28 (t, J=8.0Hz, 2H, aryl-H), 7.23-7.13 (m, 3H, aryl-H), 7.13-7.06 (m, 2H, aryl-H), 7.00-6.91 (m, 2H, aryl-H), 2.89 (s, 4H, Ph-CH2CH2).13CNMR(101MHz,CDCl3) δ=161.4 (d, J=243.4Hz, aryl-C), 141.5 (aryl-C), 137.4 (d, J=3.2Hz, aryl-C), 129.9 (d, J=7.7Hz, aryl-C), 128.6 (aryl-C), 128.5 (aryl-C), 126.1 (aryl-C), 115.1 (d, J=21.0Hz, aryl-C), 38.1 (PhCH2CH2),37.2(PhCH2).19FNMR(376MHz,CDCl3)δ-117.3ppm.
1-nitro-3-phenethylbenzene (5b):
Brown oil (104.3mg, 92%);1HNMR(400MHz,CDCl3) δ=8.00-8.03 (m, 2H, aryl-H), 7.44-7.36 (m, 2H, aryl-H), 7.24-7.29 (m, 2H, aryl-H), 7.17-7.21 (m, 1H, aryl-H), 7.16-7.12 (m, 2H, aryl-H), 3.04-2.97 (m, 2H), 2.96-2.80 (m, 2H).13CNMR(101MHz,CDCl3)δ148.2,143.6,140.6(aryl-C),134.9(aryl-C),129.2(aryl-C),128.5(aryl-C),128.5(aryl-C),126.3(aryl-C),123.3(aryl-C),121.2(aryl-C),37.4(ArCH2).
2-(3-methylphenethyl) pyridine (5c):
Pale yellow oil (72.2mg, 72%);1HNMR(400MHz,CDCl3) δ=8.44-8.47 (m, 2H, aryl-H), 7.44 (d, J=7.8Hz, 1H, aryl-H), 7.18 (t, J=6.7Hz, 2H, aryl-H), 7.06-6.93 (m, 3H, aryl-H), 2.94-2.86 (m, 4H, CH2CH2),2.33(s,3H,PhCH3).13CNMR(101MHz,CDCl3)δ150.0(aryl-C),147.5(aryl-C),140.8(aryl-C),138.0(aryl-C),136.9(aryl-C),135.9(aryl-C),129.3(aryl-C),128.3(aryl-C),126.9(aryl-C),125.4(aryl-C),123.2(aryl-C),37.4,35.0,21.4(PhCH3).HRMS-ESI(m/z):Calcdfor[(C14H15N+H)+], 198.1277; Found:198.1281.
1-methoxy-4-(5-methylhex-5-en-1-yl) benzene (5d):
Colorless oil (94.9mg, 93%);1HNMR(400MHz,CDCl3) δ=7.13 (d, J=8.6Hz, 2H, aryl-H), 6.86 (d, J=8.6Hz, 2H, aryl-H), 4.76-4.69 (m, 2H, C=CH2),3.81(s,3H,OCH3),2.65-2.57(m,2H,PhCH2), 2.08 (t, J=7.5Hz, 2H, CH2=CCH2),1.74(s,3H,CH2=CCH3),1.58-1.67(m,2H),1.56-1.46(m,2H).13CNMR(101MHz,CDCl3)δ157.6(aryl-C),146.0(CH2=C), 134.8 (aryl-C), 129.3 (aryl-C), 113.7 (aryl-C), 109.8 (C=CH2),55.2(OCH3),37.7(CH2=CCH2),34.9(PhCH2),31.4(PhCH2CH2),27.2(CH2=CCH2CH2),22.4(CH2=CCH3).HRMS-EI(m/z):Calcdfor[C14H20O+], 204.1514; Found:204.1513.
1-(2-(cyclohex-3-en-1-yl) ethyl)-3-nitrobenzene (5e):
Brown oil (79.2mg, 69%);1HNMR(400MHz,CDCl3) δ=8.01-8.06 (m, 2H, aryl-H), 7.51 (d, J=7.6Hz, 1H, aryl-H), 7.43 (t, J=7.8Hz, 1H, aryl-H), 5.62-5.70 (m, 2H, CH=CH), 2.76 (t, J=7.8Hz, 2H, PhCH2),2.02-2.20(m,3H),1.83-1.55(m,5H),1.25-1.31(m,1H).13CNMR (101MHz,CDCl3)δ144.9,134.7,129.1,127.1,126.2,123.1,120.9,38.1,33.1,33.0,31.7,28.7,25.1.HRMS-EI(m/z):Calcdfor[C14H17NO2+], 231.1259;Found:231.1260.
(2-(cyclohex-3-en-1-yl) ethyl) benzene (5f):
Colorless oil (73.1mg, 78%);1HNMR(400MHz,CDCl3) δ=7.36-7.29 (m, 2H, aryl-H), 7.27-7.19 (m, 3H, aryl-H), 5.76-5.68 (m, 2H, CH=CH), 2.71 (t, J=7.8Hz, 2H, PhCH2),2.26-2.18(m,1H),2.15-2.07(m,2H),1.88-1.60(m,5H),1.38-1.29(m,1H).13CNMR(101MHz,CDCl3)δ143.0,128.4,128.3,127.1,126.5,125.6,38.6,33.3,33.2,31.9,28.9,25.3.
To sum up experimental result is visible: adopt PNN of the present invention part-cobalt complex as catalyst, pinacol is as borane reagent, can make the aryl olefin with α position double bond that the selective hydroboration of end position double bond only occurs, and the equal highly significant of catalysis activity and selectivity, the hydroboration product being obtained by reacting need not separate, it is possible to direct and chlorinated aromatic hydrocarbons realizes coupling.
Comparative example:
This comparative example compares ferrum and the cobalt complex activity in aliphatic alkene and aromatic olefin hydroboration, and result is summed up in Table 1. As can be seen from Table 1, iron complex (tBu-PNN)FeCl2C has extraordinary activity (route 1) in the hydroboration of aliphatic alpha-olefin, but for aryl ethylene, has dehydrogenation boronation product and generate (route 2) when making solvent with toluene or THF. We with 1% complex A as catalyst precarsor, the NaHBEt of 2%3Having attempted as activator, for 2a in THF solution, reacted 1 hour under room temperature, generate anti-Markovnikov addition product 4a, productivity is up to 93% (route 3). But for aliphatic alkene 1a, the hydroboration product of generation only has 75% (route 4). When we adopt complexation B as catalyst, complex B has higher activity in aliphatic alkene or the hydroboration of aromatic olefin. Having only to the catalyst precarsor of 0.05mol%, react 15min, raw material can convert (route 5 and 6) completely. The minimum amount of complex B can be reduced to 0.01mol%, and reaction still has the product of 95% to generate (entry7). In the two example, all without other products by GC/MS and1HNMR detects. Therefore the catalyst system and catalyzing of PNN part-cobalt complex is compared the system of ferrum and is had higher activity. 1a and 2a has also been attempted by we with complex D, has activity (route 8) preferably for 1-nonene 1a, D, but for styrene 2a, only generates the hydroboration product of 48%, also has the dehydrogenation product of 52% to form (route 9).
Table 1:PNN part-iron complex/cobalt complex comparison in alkene hydroboration[a]
[a] reaction condition: HBPin (0.5mmol), 5a or 6a (0.5mmol), THF (1mL) are as solvent, reaction temperature 25 DEG C; [b] productivity be isolated yield except as otherwise noted; [c] Data Source is in ref10; [d] containing 52% dehydrogenation product, productivity is nuclear-magnetism productivity, with sym-trimethylbenzene. make in mark.
To sum up experiment is visible: the hydroboration of monoolefine is had excellent catalysis activity by PNN part-cobalt complex provided by the invention, has significance progress relative to prior art.
Finally it is necessary described herein: above-described embodiment is served only for technical scheme is described in more detail; it is not intended that limiting the scope of the invention, some nonessential improvement and adjustment that those skilled in the art makes according to the foregoing of the present invention belong to protection scope of the present invention.

Claims (10)

1. PNN part-cobalt complex catalyst, it is characterised in that be the compound with below formula:
In formula: R is C1～C30Alkyl or C6～C30Aryl; R1、R2、R3、R4、R5、R6、R7It is independently selected from hydrogen atom, halogen atom, C1-C30Alkyl, C1-C30Oxy radical, C1-C30Sulfur-containing group, C1-C30Nitrogen-containing group, C1-C30Phosphorus-containing groups, C1-C30Silicon-containing group or other safing function group, above-mentioned group is identical or different to each other, and wherein adjacent group each other in key cyclization or does not become key cyclization;X is halogen atom or C1～C30Alkyl; M is cobalt.
2. the method for PNN part-cobalt complex catalyst that a kind is prepared described in claim 1, it is characterised in that be by PNN part and MX2Or Py2MX2Carrying out complexation reaction, reaction expression is as follows:
When X is halogen atom:
When X is C1～C30Alkyl time:
3. method as claimed in claim 2, it is characterised in that described complexation reaction includes following operation:
A) preparation MX2Or Py2MX2Organic solution and the organic solution of PNN part;
B) control, at 20～30 DEG C, the organic solution of PNN part to be added dropwise over MX2Or Py2MX2Organic solution in;
C) drip finish, at room temperature stirring reaction;
D) reaction terminates, and is purified post processing.
4. method as claimed in claim 3, it is characterised in that: described organic solution is tetrahydrofuran solution, diethyl ether solution, tertbutyl ether solution, hexane solution, pentane solution or toluene solution.
5. method as claimed in claim 3, it is characterised in that: MX2Or Py2MX2The molar concentration of organic solution be 0.01 mol/L～0.1 mol/L; The molar concentration of the organic solution of PNN part is 0.1 mol/L～1.0 mol/L; PNN part and MX2Or Py2MX2Mol ratio be 1:1～2:1.
6. the application of the PNN part-cobalt complex catalyst described in a claim 1, it is characterised in that: as the catalyst of the hydroboration of monoolefine.
7. apply as claimed in claim 6, it is characterised in that: the hydroboration of described monoolefine refers to the hydroboration only occurring in α position double bond.
8. apply as claimed in claim 7, it is characterised in that: described hydroboration refers to that the alkene with α position double bond is using described PNN part-cobalt complex as catalyst, using pinacol borine (HBPin) as borane reagent, at NaHBEt3Under existence, there is the hydroboration of α position double bond.
9. apply as claimed in claim 8, it is characterised in that described hydroboration includes following operation:
1. make PNN part-cobalt complex, there is the alkene of α position double bond, pinacol borine (HBPin) and NaHBEt3At room temperature stirring reaction 10～30 minutes;
2. reaction system is exposed cancellation in atmosphere, is then purified post processing.
10. apply as claimed in claim 9, it is characterised in that: the mol ratio of the alkene and pinacol borine with α position double bond is 1:1～2:1; The mol ratio of described PNN part-cobalt complex and pinacol borine is 0.00005:1～0.05:1; NaHBEt3It is 2:1～3:1 with the mol ratio of described PNN part-cobalt complex.
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