CN105665025B - A kind of PNN parts cobalt complex catalyst and its preparation method and application - Google Patents

A kind of PNN parts cobalt complex catalyst and its preparation method and application Download PDF

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CN105665025B
CN105665025B CN201610005350.6A CN201610005350A CN105665025B CN 105665025 B CN105665025 B CN 105665025B CN 201610005350 A CN201610005350 A CN 201610005350A CN 105665025 B CN105665025 B CN 105665025B
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cobalt complex
complex catalyst
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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 kind of PNN parts cobalt complex catalyst and its preparation method and application.The catalyst is the compound for having below formula：Wherein：M is cobalt, R 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 groups；X is halogen atom or C1~C30Alkyl.The preparation of the catalyst is by PNN parts and MX2Or Py2MX2Carry out complexation reaction.PNN parts cobalt complex provided by the invention has extraordinary catalytic activity to the hydroboration of monoolefine.

Description

A kind of PNN parts-cobalt complex catalyst and its preparation method and application
Technical field
It is to be related to specifically the present invention relates to a kind of PNN parts-cobalt complex catalyst and its preparation method and application A kind of cobalt complex catalyst of three flute profile PNN parts containing electron and preparation method thereof is anti-in the hydroboration of monoolefine with it Application in answering, belongs to technical field of organic chemistry.
Background technology
Organic boronic and its derivative are widely used in organic synthesis frequently as intermediate, such as, Suzuki- Miyaura reacts can by organoboron compound C (sp3) be coupled to form C-C keys with halogenated hydrocarbons.Organic boronic acid derivative is the same as it Its organometallic nucleophiles is compared with unique stability, and can is isolated and purified and stored up many borates in atmosphere Deposit.The method that a variety of synthesis organic boric acid esters have been developed in scientists.The conventional method of one of which is to turn halogenated hydrocarbons Turn to organolithium reagent or RMgBr, the compound of the organometallic reagent of generation again with boracic is reacted to prepare organic boronic Ester, but this method due to functional group compatibility it is poor, in course of reaction again generate a large amount of inorganic salts, very not high synthesis valency Value.Recently, Hartwig et al., which has developed, a kind of is used as catalyst, alkane and B by the use of Rh2Pin2Reaction directly generates organic boric acid ester Method, but reaction condition is relatively harsh.Not long ago Liu, Marder and Steel et al. report a kind of relatively mild side again Method, they are catalyst, halogenated hydrocarbons and B with copper2Pin2Reaction generation organic boric acid ester, but this method needs excess B2Pin2, and there are substantial amounts of inorganic salts to produce.
In addition, organic boric acid ester can be prepared by Rh or Ir catalyzed alkenes hydroboration.Although dialkyl group boron Can be with the direct addition of alkene energy, but dialkoxy borine, under no catalysts conditions, reaction is very slow.Metal catalytic Hydroboration can occur under very mild conditions, and have very high Atom economy, be a kind of effective synthesizing mean.Than Such as, Wilkinson catalyst has been widely used for the hydroboration of a variety of alkene, but is often associated with a variety of side reactions, such as Alkene takes off Hydroboration, hydrogenation etc..Another weak point is during aryl ethylene hydroboration, particularly with frequency When that alcohol borine is as borane reagent, regioselectivity is poor.Secondly, the purity of Wilkinson catalyst has very big to reactivity Influence, it is especially careful that operation needs.Furthermore in many reactions, for the conversion ratio that has obtained, it is necessary to add more Rh and This kind of expensive catalyst of Ir.
It is expensive because noble metal reserves are few, and due to environmental considerations, in the last few years, scientists examination Rich reserves, cheap base metal replacement noble metal are used for organic catalytic reaction on the figure earth.In past ten years In, the complex compound of metal receives significant attention in homogeneous catalysis field.Recently, Ritter et al. reports '-imine pyridinyl and matched somebody with somebody The complex compound of the iron of body have to the hydroboration of 1,3- diene preferably activity (J.Am.Chem.Soc.2009,131, 12915).But the cobalt complex of the three flute profile PNN parts containing electron and its as catalyst in more common monoolefine Application in hydroboration is up to the present there is not yet any report.
The content of the invention
It is an object of the invention to provide a kind of PNN parts-cobalt complex catalyst and its preparation method and application, for catalysis Agent field increases a kind of cheap, environment-friendly, 100% atom validity, gentle reaction condition, simple separation side Method, good functional group compatibility and the hydroboration to monoolefine have the cobalt complex catalyst of excellent activity.
PNN parts-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 original Son, halogen atom, C1-C30Alkyl, C1-C30Oxy radical, C1-C30Sulfur-containing group, C1-C30Nitrogen-containing group, C1-C30 Phosphorus-containing groups, C1-C30Silicon-containing group or other safing function groups, above-mentioned group is identical or different to each other, wherein Bonding is cyclic each other or bonding is not cyclic for adjacent group；X is halogen atom or C1~C30Alkyl；M is cobalt.
As a kind of preferred scheme, 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 for preparing above-mentioned PNN parts-cobalt complex catalyst, is by PNN parts and MX2Or Py2MX2Carry out Complexation reaction, reaction expression are as follows：
When X is halogen atom：
When X is C1~C30Alkyl when：
As a kind of preferred scheme, the complexation reaction includes following operation：
A) MX is prepared2Or Py2MX2Organic solution and PNN parts organic solution；
B) at 20~30 DEG C MX is added dropwise in the organic solution of PNN parts by control2Or Py2MX2Organic solution in；
C) drop finishes, and reaction is stirred at room temperature；
D) reaction terminates, and carries out purifying post processing.
As further preferred scheme, described organic solution is that tetrahydrofuran solution, diethyl ether solution, tertbutyl ether are molten Liquid, hexane solution, pentane solution or toluene solution.
As further preferred scheme, MX2Or Py2MX2The molar concentration of organic solution rub for 0.01 mol/L~0.1 You/liter；The molar concentration of the organic solution of PNN parts is the mol/L of 0.1 mol/L~1.0；PNN parts and MX2Or Py2MX2 Mol ratio be 1:1~2:1.
A kind of application of described PNN parts-cobalt complex catalyst, is used as the catalysis of the hydroboration of monoolefine Agent.
As a kind of preferred scheme, the hydroboration of described monoolefine refers to that the hydroboration that α positions double bond only occurs is anti- Should.
As further preferred scheme, the alkene that described hydroboration refers to have α positions double bond is with described PNN Part-cobalt complex as catalyst, using pinacol borine (HBPin) as borane reagent, in NaHBEt3In the presence of, α positions occur The hydroboration of double bond.
As still more preferably scheme, described hydroboration includes following operation：
1. make PNN parts-cobalt complex, there is alkene, pinacol borine (HBPin) and the NaHBEt of α positions double bond3In room The lower stirring reaction of temperature 10~30 minutes；
2. reaction system exposure is quenched in atmosphere, purifying post processing is then carried out.
The condition of above-mentioned hydroboration is preferably：
The mol ratio of alkene and pinacol borine with α positions double bond is 1:1, described PNN part-cobalt complex and frequency The mol ratio of that alcohol borine is 0.00005:1~0.01:1, NaHBEt3Mol ratio with described PNN parts-cobalt complex is 2:1；Described hydroboration is carried out in solvent-free lower progress or in tetrahydrofuran, toluene, n-hexane or ether.
The described alkene with α positions double bond can be with below formula：Represent, the R in formula8 Represent any alkyl or the alkyl with various organo-functional groups, the functional group include silane, ether, ketal, amine, acid amides, ester, Ketone etc.；Ar in formula represents aryl or the aryl with substituents such as alkyl, alkoxy, ester group, halogen atoms.
The prominent effect of the present invention, it is to carry out monoene using PNN parts of the present invention-cobalt complex catalyst Hydroboration product obtained by hydrocarbon hydroboration be not required to it is to be separated, can directly and chlorinated aromatic hydrocarbons realize coupling reaction.
Described coupling reaction refers to chlorinated aromatic hydrocarbons class compound and above-mentioned hydroboration product, with Pd (OAc)2And Ruphos Cross-coupling reaction is realized as catalyst, using potassium tert-butoxide as alkali；Including following operation：
In atmosphere, by Pd (OAc)2,KOtBu and Ruphos parts are added in tube sealing, argon gas are substituted three times, then by first The hydroboration product that benzene, water, chlorinated aromatic hydrocarbons and above-mentioned hydroboration directly obtain is added in tube sealing by syringe, Ran Hou 24h is stirred at 80 DEG C；Reaction solution is filtered with diatomite, and washed with ethyl acetate, solvent is spin-dried for and obtains crude product；By crude product Further column chromatography for separation, produces coupled product.
Preferably, the mol ratio of described hydroboration product and chlorinated aromatic hydrocarbons is 1:1, Pd (OAc)2With it is described Hydroboration product molar ratio is 0.02:1, Ruphos with described hydroboration product molar ratio be 0.04:1；KOtBu with it is described Hydroboration product molar ratio is 3:1.
Compared with prior art, the present invention also has following remarkable result：
1st, the preparation method of PNN parts-cobalt complex provided by the invention is simple, and raw material is cheap and easy to get, environmentally friendly, Reaction condition is gentle, and yield is higher, and post processing is simple, is easy to scale.
2nd, PNN parts-cobalt complex provided by the invention is effective with 100% atom to the hydroboration of monoolefine Property and good functional group compatibility；
3rd, PNN parts-cobalt complex provided by the invention has excellent catalytic activity to the hydroboration of monoolefine, Not only selectivity is good, and yield is high, and reaction condition is gentle.
Embodiment
The present invention is made with reference to embodiment further in detail, intactly to illustrate.PNN parts used are in embodiment Method is prepared described in reference literature J.Am.Chem.Soc.2010,132,16756.
Embodiment 1:Prepare PNN parts-cobalt complex
(tBu-PNN)CoCl2(complex compound A)：
In glove box, by CoCl2(260mg, 2.0mmol, 1.0equiv) and THF (50mL) add 100mLschlenk Guan Zhong, then slowly willtThe THF solution (10mL) of Bu-PNN parts (628mg, 2.0mmol, 1.0equiv) is added dropwise above-mentioned molten Liquid, the gradual blackening of reaction solution color.After 24h is stirred at room temperature in reaction, with oil pump concentration of reaction solution to 10mL, add Et2O, treat that solid separates out, filter and washed with ether, drain solvent and obtain purple powder (826mg, 93%).Then by above-mentioned powder Last (50mg), is dissolved in CH2Cl2(3mL), 1mL CH are added on solution upper strata2Cl2With the mixed solvent (1 of n-hexane:1) as slow Layer is rushed, mixed solvent upper strata adds a large amount of n-hexanes, stands a couple of days, treats that n-hexane is slowly diffused into the CH of complex compound2Cl2It is molten In liquid, atropurpureus crystal is obtained, for single crystal diffraction.
1H NMR(CDCl3,400MHz)δ123.37,86.98,67.83,64.98,43.57,40.69,25.36,- 2.97,-4.70；Anal.Calcd for C19H27Cl2CoN2P:C,51.37；H,6.13；N,6.31.Found:C,51.45；H, 6.19；N,6.32.
(iPr-PNN)CoCl2(complex compound B)：
In glove box, by CoCl2(260mg, 2.0mmol, 1.0equiv) and THF (50mL) add 100mL In Schlenk pipes, then slowly williThe THF solution (10mL) of Pr-PNN parts (573mg, 2.0mmol, 1.0equiv) adds dropwise Enter above-mentioned solution, the gradual blackening of reaction solution color.After 24h is stirred at room temperature in reaction, with oil pump concentration of reaction solution to 10mL, then Add Et2O, treat that solid separates out, filter and washed with ether, drain solvent and obtain brown ceramic powder (622mg, 75%).Then will be upper Powder (50mg) is stated, is dissolved in CH2Cl2(3mL), 1mL CH are added on solution upper strata2Cl2With the mixed solvent (1 of n-hexane:1) make For cushion, mixed solvent upper strata adds a large amount of n-hexanes, stands a couple of days, treats that n-hexane is slowly diffused into complex compound CH2Cl2In solution, black crystals are obtained, for single crystal diffraction.
1H NMR(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.Calcd for C17H23Cl2CoN2P+H2O:C,47.02；H,5.80；N, 6.45.Found:C,46.96；H,5.59；N,6.41.
(iPr-PNN) CoCH2SiCH3 (complex compound D)：
In glove box, Py2Co (CH2SiCH3) 2 (392mg, 1.0mmol, 1.0equiv) and pentane (10mL) are added Enter in 25mL Schlenk pipes, then slowly by the pentane solution of iPr-PNN parts (286mg, 1.0mmol, 1.0equiv) Above-mentioned solution is added dropwise in (5mL).Reaction is stirred at room temperature 1 hour, filters to obtain dark solution with diatomite, oil pump is drained molten Agent, 5ml pentanes are added, are placed at -35 DEG C the black solid powder (263mg, 51%) recrystallized.1H NMR(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:Complex compound B described in embodiment 1 tests to the catalytic activity of the hydroboration of different monoolefines
By taking alkene 1a hydroboration process as an example：First in glove box, by complex compound B (2.1mg), THF (20mL) and NaBEt3H (1M) (10uL) is added in 50ml conical flasks and is obtained the catalyst solution of purple；Then by alkene 1a (63mg, 0.5mmol, 1equiv) and HBpin (75uL, 0.5mmol, 1equiv) add in 8mL reaction bottle, then take what is configured to urge Agent solution 1mL is added in above-mentioned reaction bottle；After 15min is stirred at room temperature in reaction, it is quenched in air；Then revolve Solvent is evaporated off, rapid column chromatography (mixture of the high about 5cm of silica gel, petroleum ether and ethyl acetate makees eluant, eluent) obtains colourless liquid 3a.3b~3n, 4b~4m preparation method with 3a preparation method.
4,4,5,5-tetramethyl-2-nonyl-1,3,2-dioxaborolane(3a)：
Colourless liquid (121.0mg, 95%)；1H NMR(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).13C NMR(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%)；1H NMR(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).13C NMR(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%)；1H NMR(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).13C NMR(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%)；1H NMR(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).13C NMR(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%)1H NMR(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,CH2CH2), B 0.72 (t, J=8.2Hz, 2H, CH2B).13C NMR(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%)；1H NMR(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).13C NMR (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%)；1H NMR(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).13C NMR(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):Calcd for[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%)；1H NMR(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).13C NMR (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):Calcd for[(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%)；1H NMR(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).13C NMR(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):Calcd for [(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%)；1H NMR(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).13C NMR(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):Calcd for[(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%)；1H NMR(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).13C NMR (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):Calcd for[(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%)；1H NMR(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).13C NMR(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):Calcd for[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%)；1H NMR(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).13C NMR(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):Calcd for[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%)；1H NMR(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).13C NMR(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):Calcd for[C13H25BO2+],223.1984；found:223.1987.
4,4,5,5-tetramethyl-2-phenethyl-1,3,2-dioxaborolane(4a)：
Colourless liquid (106.0mg, 91%)；1H NMR(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).13C NMR(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%)；1H NMR(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).13C NMR(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%)；1H NMR(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).13C NMR(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):Calcd for [C15H23BO2+],245.1827,found:245.1830.
2-(4-methoxyphenethyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane(4d)：
Colourless liquid (126.0mg, 96%)；1H NMR(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).13C NMR(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%)；1H NMR(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).13C NMR(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):Calcd for[C18H29BO3+],303.2246；found:303.2249.
2-(4-fluorophenethyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane(4f)：Colourless liquid (121.0mg, 97%)；1H NMR(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).13C NMR(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).19F NMR(376MHz,CDCl3)δ-118.4.
2-(3-fluorophenethyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane(4g)：
Colourless liquid (111.0mg, 89%)；1H NMR(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).13C NMR (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).19F NMR (376MHz,CDCl3)δ-114.2.HRMS-EI(m/z):Calcd for[C14H20BO2F+],249.1577；found: 249.1576.
2-(4-chlorophenethyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane(4h)：Colourless liquid (120.0mg, 90%)；1H NMR(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).13C NMR(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%)；1H NMR(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).13C NMR(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)phenyl acetate(4j)：
Colourless liquid (116.0mg, 80%)；1H NMR(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).13C NMR (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): Calcd for[(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%)；1H NMR(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).13C NMR (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):Calcd for[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%)；1H NMR(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).13C NMR(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%)；1H NMR(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).13C NMR(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 compound B (1.0mg) and NaBEt3H (1M) (5uL) is added in 8mL reaction bottle.After 1h is stirred at room temperature in reaction, exposed to air In be quenched.Rapid column chromatography (mixture of the high about 5cm of silica gel, petroleum ether and ethyl acetate makees eluant, eluent) obtains colourless liquid 4a (m =11.5g, yield 99%).
4,4,5,5-tetramethyl-2-phenethyl-1,3,2-dioxaborolane(4a)：
Colourless liquid (106.0mg, 91%)；1H NMR(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).13C NMR(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 gained borate of embodiment 2 and the conjugation of chlorinated aromatic hydrocarbons compound
In atmosphere, by Pd (OAc)2(2.2mg,0.01mmol),KOtBu (168.0mg, 1.5mmol) and Ruphos parts (9.3mg, 0.02mmol) is added in 10mL tube sealings, argon gas is substituted three times, then by toluene (1.5mL), water (0.15mL), chlorobenzene (56.0mg, 0.50mmol), and the borate 4f (125.1mg, 0.50mmol, 1.0equiv) that reaction directly obtains pass through injection Device is added in tube sealing, is reacted and is stirred 24h at 80 DEG C.Then reaction solution is filtered with diatomite, and with ethyl acetate (5 × 5mL) wash, be spin-dried for solvent and obtain crude product.The further column chromatography for separation of crude product is obtained into white solid 5a (85.8mg, 86%) .5b the preparation method of~5f preparation method with 5a.
1-fluoro-4-phenethylbenzene(5a)：
1H NMR(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).13C NMR (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).19F NMR(376MHz,CDCl3)δ- 117.3ppm.
1-nitro-3-phenethylbenzene(5b)：
Brown oil (104.3mg, 92%)；1H NMR(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).13C NMR(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%)；1H NMR(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).13C NMR(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):Calcd for[(C14H15N+H)+],198.1277；found:198.1281.
1-methoxy-4-(5-methylhex-5-en-1-yl)benzene(5d)：
Colorless oil (94.9mg, 93%)；1H NMR(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).13C NMR(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):Calcd for[C14H20O+], 204.1514；found:204.1513.
1-(2-(cyclohex-3-en-1-yl)ethyl)-3-nitrobenzene(5e)：
Brown oil (79.2mg, 69%)；1H NMR(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).13C NMR(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):Calcd for[C14H17NO2+],231.1259；found:231.1260.
(2-(cyclohex-3-en-1-yl)ethyl)benzene(5f)：
Colorless oil (73.1mg, 78%)；1H NMR(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).13C NMR(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：Made using PNN parts-cobalt complex of the present invention as catalyst, pinacol For borane reagent, can make to have the aryl olefin of α positions double bond only to occur the selective hydroboration of end position double bond, and catalytic activity and The equal highly significant of selectivity, the hydroboration product for reacting to obtain are not required to be separated, directly can be coupled with chlorinated aromatic hydrocarbons realization.
Comparative example：
This comparative example compares the activity of iron and cobalt complex in aliphatic olefin and aromatic olefin hydroboration, As a result it is summarised in table 1.As can be seen from Table 1, iron complex (tBu-PNN)FeCl2C is anti-in the hydroboration of aliphatic alpha-olefin Have in answering extraordinary active (route 1), but for aryl ethylene, the production of dehydrogenation boronation is had when making solvent with toluene or THF Thing generates (route 2).We are used as catalyst precarsor, 2% NaHBEt by the use of 1% complex compound A3Tasted as activator Examination, for 2a in THF solution, reacts 1 hour under normal temperature, generates anti-Markovnikov addition product 4a, and yield is up to 93% (route 3).But for aliphatic olefin 1a, the hydroboration product of generation only has 75% (route 4).When us using complexing B as catalysis During agent, complex compound B has higher activity in the hydroboration of aliphatic olefin or aromatic olefin.Only need 0.05mol% catalyst precarsor, reacts 15min, and raw material can convert (route 5 and 6) completely.Complex compound B minimum amount 0.01mol% can be reduced to, reaction still has 95% product generation (entry 7).In the two examples, all without other Product by GC/MS and1H NMR are detected.Therefore the catalyst system and catalyzing of PNN parts-cobalt complex has more compared to the system of iron High activity.We are also attempted 1a and 2a with complex compound D, and for 1- nonenes 1a, D has preferably active (route 8) 48% hydroboration product, but for styrene 2a, is only generated, also 52% dehydrogenation product forms (route 9).
Table 1：PNN parts-comparison of the iron complex/cobalt complex in alkene hydroboration[a]
[a] reaction condition：HBPin (0.5mmol), 5a or 6a (0.5mmol), THF (1mL) are used as solvent, reaction temperature 25℃；[b] yield is to separate yield unless otherwise indicated；[c] data source is in ref 10；[d] containing 52% dehydrogenation product, Yield is nuclear-magnetism yield, makees internal standard with mesitylene.
To sum up test visible：PNN parts-cobalt complex provided by the invention has excellent to the hydroboration of monoolefine Catalytic activity, there is conspicuousness progress relative to prior art.
Finally be necessary described herein be：Above-described embodiment is served only for further detailed to technical scheme work Ground explanation, it is impossible to be interpreted as limiting the scope of the invention, those skilled in the art is according to the above of the invention Some the nonessential modifications and adaptations made belong to protection scope of the present invention.

Claims (9)

1. a kind of application of PNN parts-cobalt complex catalyst, described PNN parts-cobalt complex catalyst is with as follows The compound of formula：
In formula：R is C1~C30Alkyl or C6~C30Aryl；R1、R2、R3、R4、R5、R6、R7It is independently selected from hydrogen atom, halogen Plain atom, C1-C30Alkyl, C1-C30Oxy radical, C1-C30Sulfur-containing group, C1-C30Nitrogen-containing group, C1-C30Contain Phosphorus group, C1-C30Silicon-containing group or other safing function groups, above-mentioned group is identical or different to each other, wherein adjacent Bonding is cyclic each other or bonding is not cyclic for group；X is halogen atom or C1~C30Alkyl；M is cobalt；It is characterized in that：With institute State the catalyst of hydroboration of the PNN parts-cobalt complex catalyst as monoolefine.
2. the application of PNN parts-cobalt complex catalyst as claimed in claim 1, it is characterised in that described PNN parts- The preparation method of cobalt complex catalyst, it is by by PNN parts and MX2Or Py2MX2Complexation reaction is carried out, reaction expression is as follows It is shown：
When X is halogen atom：
When X is C1~C30Alkyl when：
3. the application of PNN parts-cobalt complex catalyst as claimed in claim 2, it is characterised in that the complexation reaction bag Include following operation：
A) MX is prepared2Or Py2MX2Organic solution and PNN parts organic solution；
B) at 20~30 DEG C MX is added dropwise in the organic solution of PNN parts by control2Or Py2MX2Organic solution in；
C) drop finishes, and reaction is stirred at room temperature；
D) reaction terminates, and carries out purifying post processing.
4. the application of PNN parts-cobalt complex catalyst as claimed in claim 3, it is characterised in that：Described organic solution For tetrahydrofuran solution, diethyl ether solution, tertbutyl ether solution, hexane solution, pentane solution or toluene solution.
5. the application of PNN parts-cobalt complex catalyst as claimed in claim 3, it is characterised in that：MX2Or Py2MX2Have The molar concentration of machine solution is the mol/L of 0.01 mol/L~0.1；The molar concentration of the organic solution of PNN parts is rubbed for 0.1 You/liter~1.0 mol/Ls；PNN parts and MX2Or Py2MX2Mol ratio be 1:1~2:1.
6. the application of PNN parts-cobalt complex catalyst as claimed in claim 1, it is characterised in that：The boron of the monoolefine Hydrogenation refers to the hydroboration for only occurring in α positions double bond.
7. the application of PNN parts-cobalt complex catalyst as claimed in claim 6, it is characterised in that：Described hydroboration is anti- Should refer to have the alkene of α positions double bond using described PNN parts-cobalt complex as catalyst, with pinacol borine (HBPin) as borane reagent, in NaHBEt3In the presence of, the hydroboration of generation α positions double bond.
8. the application of PNN parts-cobalt complex catalyst as claimed in claim 7, it is characterised in that described hydroboration is anti- Following operation should be included：
1. make PNN parts-cobalt complex, there is alkene, pinacol borine (HBPin) and the NaHBEt of α positions double bond3At room temperature Stirring reaction 10~30 minutes；
2. reaction system exposure is quenched in atmosphere, purifying post processing is then carried out.
9. the application of PNN parts-cobalt complex catalyst as claimed in claim 8, it is characterised in that：With α positions double bond The mol ratio of alkene and pinacol borine is 1:1~2:1；The mol ratio of described PNN parts-cobalt complex and pinacol borine For 0.00005:1~0.05:1；NaHBEt3Mol ratio with described PNN parts-cobalt complex is 2:1~3:1.
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