CN1792452A - Metal complex catalyst of chiral spirocyclo mono-phosphorus (phosphine) ligand and nickel, its prepn. method and application - Google Patents
Metal complex catalyst of chiral spirocyclo mono-phosphorus (phosphine) ligand and nickel, its prepn. method and application Download PDFInfo
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Abstract
A metal complex as catalyst with wide range of application is prepared from chiral spirocyclic mono-phosphorus (mono-phosphine) ligand and Ni. It can be used in asymmetrical olefinic hydrogenation reaction to obtain a compound with chiral center. Its preparing process is also disclosed.
Description
Technical field
The present invention relates to the novel nickel metal complex catalyst of a class, be to disclose novel metal complexes and preparation method that a class forms with chiral spirocyclo mono-phosphorus (phosphine) part and nickel specifically, and the application of this metalloid complex compound in the asymmetric alkene hydrogenation of catalysis.
Background technology
Asymmetry catalysis is synthetic to be focus (Ohkuma, T. in the current Synthetic Organic Chemistry research field; Kitamura, M.; Noyori, R.Catalytic Asymmetric Synthesis, Wiley, New York, 2000).The synthetic key of asymmetry catalysis is how to design and synthesize high enantioselectivity and high catalytic activity catalyst.The catalyst system of having developed at present of obtaining immense success has promoted the industrial applications of asymmetric catalysis greatly, has created huge economic benefit.For example, 1975, the rhodium catalytic system that Knowles will contain biphosphine ligand DIPAMP successfully was used for industrial production (Knowles, W.S.Acc.Chem.Res.1983,16,106 of L-Dopa (a kind of specific drug for the treatment of Parkinsonism); Knowles, W.S.J.Chem.Ed.1986,63,222).And for example, two phosphine diamine ruthenium catalyst systems of exploitations such as R.Noyori have obtained extraordinary enantioselectivity and very high turn over number in the asymmetric catalytic hydrogenation of multiple aromatic ketone, has wide industrial application prospect (Angew.Chem.Int.Ed.2001,40,40～73).
Transition metal-catalyzed alkene hydrogenation is a kind of reaction that forms carbon-carbon bond efficiently, can change into of great use compound to the simple raw material of industry.Asymmetry catalysis alkene hydrogenation has great application prospect in drug molecules such as synthetic different brufen, naproxen, therefore quite be subjected to pay attention to (RajanBabu, T.V.Chem.Rev.2003,103,2845-2860 in recent years; Franci ò, G; Faraone, F.; Leitner, W.J.Am.Chem.Soc.2002,124,736-737).But mostly the example of at present successful realization alkene hydrogenation is the assorted dimerization of aromatic radical ethene and ethene, alkene hydrogenation for the polysubstituted ethene of aromatic radical has only carried out some desk studies, reaction result poor (Fassina, the V. of existing catalyst system; Ramminger, C.; Seferin, M.; Monteiro, A.L.Tetrahedron 2000,56,7403-7409.RajanBabu, T.V.; Nomura, N.; Jin, J.; Nandi, M.; Park, H.; Sun, X.J.Org.Chem.2003,68,8431-8446).Therefore and the product types of the alkene hydrogenation gained of the polysubstituted ethene of aromatic radical is abundanter, has application prospect widely, studies new catalyst system and solves this class reaction and have very high researching value and application prospects.
Summary of the invention
Purpose of the present invention is intended to for filling up the blank of prior art, the metal complex catalyst that provides a class to be formed with nickel by chiral spirocyclo mono-phosphorus (phosphine) part; Another object of the present invention provides the preparation method of above-mentioned metal complex catalyst.This class catalyst has obtained very high chemo-selective and stereoselectivity in the alkene hydrogenation of asymmetry catalysis aromatic radical ethene and aromatic radical substituted ethylene in addition.
The present invention discloses the metal complex catalyst that class chiral spirocyclo mono-phosphorus (phosphine) part forms with nickel for achieving the above object, the cationic moiety that it is characterized in that it comprises a Ni atom, chiral spirocyclo mono-phosphorus (phosphine) part and one and has allylic group, and its structural formula is:
Wherein: n=0～3, R
0, R
1, R
2, R
3Be C
1～C
8Alkyl, substituted alkyl (substituting group is C
1～C
8Alkoxyl, haloalkyl, and ester group), phenyl, (substituting group on the phenyl is C to substituted-phenyl
1～C
8Alkyl, alkoxyl, phenyl, substituted-phenyl, substituting group quantity is 1～5), 1-naphthyl, 2-naphthyl; Z is O, CH
2Y is NR
4R
5, OR
6, R
7, [R wherein
4, R
5, R
6, R
7Be C
1～C
8Alkyl, substituted alkyl, phenyl, substituted-phenyl (substituting group on the phenyl is C
1～C
8Alkyl, alkoxyl, phenyl, substituted-phenyl, substituting group quantity is 1～5), 1-naphthyl, 2-naphthyl]; X is halide ion, C
1～C
8Carboxylate radical, BARF
-[BARF
-Be four (3, the 5-bis trifluoromethyl phenyl) borate], four (perfluor tert-butoxy) aluminium ion, four (hexafluoro isopropoxy) aluminium ion, hexafluoro-phosphate radical, hexafluoroantimonic anion, tetrafluoroborate, TFMS root.
Described alkyl is methyl, ethyl, n-pro-pyl, isopropyl, cyclopropyl, normal-butyl, isobutyl group, sec-butyl, the tert-butyl group, cyclobutyl, n-pentyl, isopentyl, neopentyl, sec-amyl, tertiary pentyl, cyclopenta, n-hexyl, isohesyl, new hexyl, Sec-Hexyl, uncle's hexyl, cyclohexyl, n-heptyl, different heptyl, new heptyl, Zhong Gengji, uncle's heptyl, suberyl, n-octyl, iso-octyl, new octyl group, secondary octyl, uncle's octyl group, ring octyl group.
Described alkoxyl be methoxyl group, ethyoxyl, positive propoxy, isopropoxy, ring propoxyl group, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, cyclobutoxy group, n-pentyloxy, isoamoxy, neopentyl oxygen, secondary amoxy, uncle's amoxy, cyclopentyloxy, just own oxygen base, dissident's oxygen base, new own oxygen base, secondary own oxygen base, the own oxygen base of uncle, cyclohexyloxy, positive heptan oxygen base, different heptan oxygen base, new heptan oxygen base, Zhong Geng oxygen base, uncle's oxygen in heptan base,
Described ester group is a methoxycarbonyl group, carbethoxyl group, the third oxygen carbonyl, the different third oxygen carbonyl, butoxy carbonyl, isobutyl boc, secondary butoxy carbonyl, tertbutyloxycarbonyl, the ring butoxy carbonyl, positive penta oxygen carbonyl, isoamyl oxygen carbonyl, new penta oxygen carbonyl, secondary penta oxygen carbonyl, uncle's penta oxygen carbonyl, encircle penta oxygen carbonyl, just own oxygen carbonyl, dissident's oxygen carbonyl, new own oxygen carbonyl, secondary own oxygen carbonyl, the own oxygen carbonyl of uncle, hexamethylene oxygen carbonyl, positive heptan the oxygen carbonyl, different heptan the oxygen carbonyl, new heptan the oxygen carbonyl, Zhong Geng oxygen carbonyl, uncle's oxygen in heptan carbonyl, ring oxygen carbonyl in heptan, positive hot oxygen carbonyl, different hot oxygen carbonyl, new hot oxygen carbonyl, Zhong Xin oxygen carbonyl, the hot oxygen carbonyl of uncle, encircle hot oxygen carbonyl.
Described chiral spirocyclo mono-phosphorus (phosphine) ligand L
*, be left-handed chiral spirocyclo mono-phosphorus (phosphine) part;
Described chiral spirocyclo mono-phosphorus (phosphine) ligand L
*, be chiral spirocyclo mono-phosphorus (phosphine) part of dextrorotation;
Described chiral spirocyclo mono-phosphorus (phosphine) ligand L
*, be chiral spirocyclo mono-phosphorus (phosphine) part of racemization.
Chiral spirocyclo mono-phosphorus of the present invention (phosphine) part is with the preparation method of the metal complex catalyst of nickel formation, it is characterized in that it is at COD (COD=1 by the Ni metal precursor, the 5-cyclo-octadiene) or chiral spirocyclo mono-phosphorus (phosphine) part that adds the allyl halide of 1～2 equivalent and 1～2 equivalent in one or more solvents in the toluene, ether stir down at 0～50 ℃ and prepared in 1～10 hour, that is:
L wherein
*It is chiral spirocyclo mono-phosphorus (phosphine) part; R
1, R
2, R
3Be C
1～C
8Alkyl, substituted alkyl (substituting group is C
1～C
8Alkoxyl, haloalkyl, and ester group), phenyl, (substituting group on the phenyl is C to substituted-phenyl
1～C
8Alkyl, alkoxyl, phenyl, substituted-phenyl, substituting group quantity is 1～5), 1-naphthyl, 2-naphthyl.
The chiral metal complex compound catalyst that the chiral metal complex compound catalyst that described preparation method obtains also can obtain having different anions by anion exchange, that is:
L wherein
*It is chiral spirocyclo mono-phosphorus (phosphine) part; R
1, R
2, R
3Be C
1～C
8Alkyl, substituted alkyl (substituting group is C
1～C
8Alkoxyl, haloalkyl, and ester group), phenyl, (substituting group on the phenyl is C to substituted-phenyl
1～C
8Alkyl, alkoxyl, phenyl, substituted-phenyl, substituting group quantity is 1～5), 1-naphthyl, 2-naphthyl; X is halide ion, C
1～C
8Carboxylate radical, BARF
-[BARF
-Be four (3, the 5-bis trifluoromethyl phenyl) borate], four (perfluor tert-butoxy) aluminium ion, four (hexafluoro isopropoxy) aluminium ion, hexafluoro-phosphate radical, hexafluoroantimonic anion, tetrafluoroborate, TFMS root.
Chiral spirocyclo mono-phosphorus of the present invention (phosphine) part is with the application of the metal complex catalyst of nickel formation, be the asymmetric alkene hydrogenation of this catalyst aromatic radical ethene and the polysubstituted ethene of aromatic radical concretely, it is characterized in that catalyst amount is 0.01～20%; Solvent is a carrene, 1, one or several in 2-dichloroethanes, toluene, the ether; Reaction temperature is-40～80 ℃; Reaction time is 1～36 hour.Reaction equation is:
Wherein: Cat
*It is the chiral metal complex compound catalyst in the claim 1; Ar is a phenyl, (substituting group on the phenyl is C to substituted-phenyl
1～C
8Alkyl, alkoxyl, alkylthio group, haloalkyl, and amino, substituted-amino, ester group, substituting group quantity is 1～5), encircle more or heterocyclic aryl (as: 1-naphthyl, 2-naphthyl, furyl, thienyl, imidazole radicals, quinolyl, indyl), the many rings that replace or heterocyclic aryl (as: substituting group is C
1～C
8Alkoxyl, haloalkyl, 1-naphthyl, 2-naphthyl, furyl, thienyl, imidazole radicals, quinolyl, indyl that ester group replaces, substituent quantity is 1～7); R
8, R
9, R
10Be C
1～C
8Alkyl, (as: substituting group is C to the alkyl of various replacements
1～C
8Alkoxyl, alkylthio group, haloalkyl), phenyl, (substituting group on the phenyl is C to substituted-phenyl
1～C
8Alkyl, alkoxyl, ester group, substituting group quantity is 1～5), encircle more or heterocyclic aryl (as: 1-naphthyl, 2-naphthyl, furyl, thienyl, imidazole radicals, quinolyl, indyl), the many rings that replace or heterocyclic aryl (as: substituting group is C
1～C
8Alkoxyl, ester group, the 1-naphthyl of replacement, 2-naphthyl, furyl, thienyl, imidazole radicals, quinolyl, indyl, substituent quantity is 1～7); Described alkyl is methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, isobutyl group, sec-butyl, the tert-butyl group, isopentyl, cyclopropyl, cyclobutyl, cyclopenta, suberyl etc.; Described alkoxyl is methoxyl group, ethyoxyl, positive propoxy, isopropoxy, n-butoxy, tert-butoxy etc.; Described haloalkyl is the haloalkyl of fluorine-containing, chlorine, bromine, iodine; Ester group is C such as methoxycarbonyl group, carbethoxyl group, the third oxygen carbonyl, the different third oxygen carbonyl, butoxy carbonyl, isobutyl boc
1-C
8Ester group.
Chirality nickel metal complex catalyst of the present invention, it is synthetic easily to pass through chiral spirocyclo mono-phosphorus (phosphine) part and nickel precursor.Because chiral spirocyclo mono-phosphorus of the present invention (phosphine) part and the formed complex compound of nickel have suitable space multistory effect and electronic effect, this class catalyst is applied in the alpha-substituted aromatic radical ethene asymmetry catalysis alkene hydrogenation, can access good chemo-selective and up to 99% enantioselectivity, and report (RajanBabu, the T.V. of the asymmetric syntheses of not reacting hereto at present; Nomura, N.; Jin, J.; Nandi, M.; Park, H.; Sun, X.J.Org.Chem.2003,68,8431-8446).What deserves to be mentioned is that the chiral product that this reaction obtains is a kind of very useful compound (Douglas, C.J. with full carbon quaternary carbon chiral centre; Overman, L.E.Proc.Nat.Acad.Sci.U.SA.2004,101,5363-6367.).
The specific embodiment
To help further to understand the present invention by following embodiment, but not limit content of the present invention.Preparation method of the present invention can be further as follows with the preparation process embodiment of representation compound:
Embodiment 1:(S, R, R)-and O, O '-[7,7 '-(1,1 '-spiro indan)]-N, the preparation of N-two 2-phenethyl phosphoramidite pi-allyl bromination nickel complexes
Under nitrogen atmosphere, with Ni (COD)
2(137.5mg, 0.5mmol) the middle 1mL COD (COD=1,5 cyclo-octadiene) that adds stirs a few minutes, and (63.5mg 0.525mmol), and stirred 5～10 minutes, obtained dark sanguine pi-allyl bromination nickel dimer to drip allyl bromide, bromoallylene down at 20 ℃ then.To wherein adding the 2mL dilution with toluene, add then (S, R, R)-and O, O '-[7,7 '-(1,1 '-spiro indan)]-N, (252mg, 4mL toluene solution 0.5mmol) continue to stir 2 hours down at 20 ℃ N-two 2-phenethyl phosphoramidites.The orange red mixture of gained is used diatomite filtration under nitrogen atmosphere, the filtrate vacuum is drained solvent.With the red solid vacuum drying that obtains 10 hours, obtain the orange red pressed powder of 332mg, yield is 97%.
Embodiment 2:(R, R, R)-and O, O '-[7,7 '-(1,1 '-spiro indan)]-N, the preparation of N-two 2-phenethyl phosphoramidite pi-allyl bromination nickel complexes
Under nitrogen atmosphere, with Ni (COD)
2(137.5mg, 0.5mmol) the middle 1mL COD (COD=1,5 cyclo-octadiene) that adds stirs a few minutes, and (63.5mg 0.525mmol), and stirred 5～10 minutes, obtained dark sanguine pi-allyl bromination nickel dimer to drip allyl bromide, bromoallylene down at 20 ℃ then.To wherein adding the 2mL dilution with toluene, add then (R, R, R)-and O, O '-[7,7 '-(1,1 '-spiro indan)]-N, (252mg, 4mL toluene solution 0.5mmol) continue to stir 2 hours down at 20 ℃ N-two 2-phenethyl phosphoramidites.The orange red mixture of gained is used diatomite filtration under nitrogen atmosphere, the filtrate vacuum is drained solvent.With the red solid vacuum drying that obtains 10 hours, obtain the orange red pressed powder of 335mg, yield is 98%.
Embodiment 3:(R)-and O, O '-[7,7 '-(1,1 '-spiro indan)]-N, the preparation of N-dimethyl phosphoramidite pi-allyl bromination nickel complex
Under nitrogen atmosphere, with Ni (COD)
2(137.5mg, 0.5mmol) the middle 1mL COD (COD=1,5 cyclo-octadiene) that adds stirs a few minutes, and (63.5mg 0.525mmol), and stirred 5～10 minutes, obtained dark sanguine pi-allyl bromination nickel dimer to drip allyl bromide, bromoallylene down at 20 ℃ then.To wherein adding the 2mL dilution with toluene, add (R)-O then, O '-[7,7 '-(1,1 '-spiro indan)]-N, (163mg, 4mL toluene solution 0.5mmol) continue to stir 2 hours down at 20 ℃ N-dimethyl phosphoramidite.The orange red mixture of gained is used diatomite filtration under nitrogen atmosphere, the filtrate vacuum is drained solvent.With the red solid vacuum drying that obtains 10 hours, obtain 247mg yellow green pressed powder, yield is 97%.
Embodiment 4:(R)-and O, O '-[7,7 '-(1,1 '-spiro indan)]-N, the preparation of N-diisopropylphosphoramidite pi-allyl bromination nickel complex
Under nitrogen atmosphere, with Ni (COD)
2(137.5mg, 0.5mmol) the middle 1mLCOD (COD=1,5 cyclo-octadiene) that adds stirs a few minutes, and (63.5mg 0.525mmol), and stirred 5～10 minutes, obtained dark sanguine pi-allyl bromination nickel dimer to drip allyl bromide, bromoallylene down at 20 ℃ then.To wherein adding the 2mL dilution with toluene, add (R)-O then, O '-[7,7 '-(1,1 '-spiro indan)]-N, the 4mL toluene solution of N-diisopropylphosphoramidite (0.5mmol) continues to stir 2 hours down at 20 ℃.The orange red mixture of gained is used diatomite filtration under nitrogen atmosphere, the filtrate vacuum is drained solvent.With the red solid vacuum drying that obtains 10 hours, obtain 275mg yellow green solid, yield is 98%.
Embodiment 5:(R)-and O, O '-[7,7 '-(1,1 '-spiro indan)]-N, the preparation of N-dicyclohexyl phosphoramidite pi-allyl bromination nickel complex
Under nitrogen atmosphere, with Ni (COD)
2(137.5mg, 0.5mmol) the middle 1mLCOD (COD=1,5 cyclo-octadiene) that adds stirs a few minutes, and (63.5mg 0.525mmol), and stirred 5～10 minutes, obtained dark sanguine pi-allyl bromination nickel dimer to drip allyl bromide, bromoallylene down at 20 ℃ then.To wherein adding the 2mL dilution with toluene, add (R)-O then, O '-[7,7 '-(1,1 '-spiro indan)]-N, the 4mL toluene solution of N-dicyclohexyl phosphoramidite (0.5mmol) continues to stir 2 hours down at 20 ℃.The orange red mixture of gained is used diatomite filtration under nitrogen atmosphere, the filtrate vacuum is drained solvent.With the red solid vacuum drying that obtains 10 hours, obtain the 314mg yellow solid, yield is 98%.
Embodiment 6:(R)-and O, the preparation of O '-[7,7 '-(1,1 '-spiro indan)]-O-phenyl phosphites pi-allyl bromination nickel complex
Under nitrogen atmosphere, with Ni (COD)
2(137.5mg, 0.5mmol) the middle 1mLCOD (COD=1,5 cyclo-octadiene) that adds stirs a few minutes, and (63.5mg 0.525mmol), and stirred 5～10 minutes, obtained dark sanguine pi-allyl bromination nickel dimer to drip allyl bromide, bromoallylene down at 20 ℃ then.To wherein adding the 2mL dilution with toluene, add (R)-O then, the 4mL toluene solution of O '-[7,7 '-(1,1 '-spiro indan)]-O-methyl phosphite ester (0.5mmol) continues to stir 2 hours down at 20 ℃.The orange red mixture of gained is used diatomite filtration under nitrogen atmosphere, the filtrate vacuum is drained solvent.With the red solid vacuum drying that obtains 10 hours, obtain the orange red solid of 269mg, yield is 97%.
Embodiment 7:(R)-and O, the preparation of O '-[7,7 '-(1,1 '-spiro indan)]-phenyl-phosphonite ester pi-allyl bromination nickel complex
Under nitrogen atmosphere, with Ni (COD)
2(137.5mg, 0.5mmol) the middle 1mLCOD (COD=1,5 cyclo-octadiene) that adds stirs a few minutes, and (63.5mg 0.525mmol), and stirred 5～10 minutes, obtained dark sanguine pi-allyl bromination nickel dimer to drip allyl bromide, bromoallylene down at 20 ℃ then.To wherein adding the 2mL dilution with toluene, add (R)-O then, the 4mL toluene solution of O '-[7,7 '-(1,1 '-spiro indan)]-methyl phosphinate (0.5mmol) continues to stir 2 hours down at 20 ℃.The orange red mixture of gained is used diatomite filtration under nitrogen atmosphere, the filtrate vacuum is drained solvent.With the red solid vacuum drying that obtains 10 hours, obtain the orange red solid of 264mg, yield is 98%.
Embodiment 8:(R)-CH
2, CH
2'-[7,7 '-(1,1 '-spiro indan)]-preparation of the inferior phosphine alkane of phenyl propyl group bromination nickel complex
Under nitrogen atmosphere, with Ni (COD)
2(137.5mg, 0.5mmol) the middle 1mL COD (COD=1,5 cyclo-octadiene) that adds stirs a few minutes, and (63.5mg 0.525mmol), and stirred 5～10 minutes, obtained dark sanguine pi-allyl bromination nickel dimer to drip allyl bromide, bromoallylene down at 20 ℃ then.To wherein adding the 2mL dilution with toluene, add (R)-O then, the 4mL toluene solution of O '-[7,7 '-(1,1 '-spiro indan)]-methyl phosphinate (0.5mmol) continues to stir 2 hours down at 20 ℃.The orange red mixture of gained is used diatomite filtration under nitrogen atmosphere, the filtrate vacuum is drained solvent.With the red solid vacuum drying that obtains 10 hours, obtain the pale brown look solid of 254mg, yield is 95%.
Embodiment 9: the asymmetric alkene hydrogenation of the metal complex to catalyze alpha-substituted aromatic radical ethene that chiral spirocyclo mono-phosphorus (phosphine) part and nickel form
(with S, R, R)-and O, O '-[7,7 '-(1,1 '-spiro indan)]-N, N-two 2-phenethyl phosphoramidite pi-allyl bromination nickel complexes and the cinnamic asymmetric alkene hydrogenation of NaBARF catalysis α-isopropyl are example)
Under nitrogen atmosphere, the 2mL carrene orange-red solution of the metallic nickel complex compound among the embodiment 1 (13.8mg 0.002mmol) is added in the 2mL carrene suspension of NaBARF complexing at room temperature 20 minutes.Introduce ethylene gas then, obtain yellow solution, drip then α-cumene ethene (29mg, 0.2mmol), 35 ℃ of stirred in water bath 2.5 hours.Reaction is used extracted with diethyl ether, anhydrous magnesium sulfate drying, n-hexane column chromatography with the cancellation of 2mL saturated ammonium chloride solution.Obtain target product 31mg, yield 89%, 99%ee.The product optical purity is with having Suplco β-DEX
TMThe GC of 120 chiral columns analyzes.
The gained experimental result sees the following form 1, and (Ar is with phenyl, p-methylphenyl, an aminomethyl phenyl, m-methoxyphenyl, p-methoxyphenyl, rubigan, 2-naphthyl; R is with ethyl, and n-pro-pyl, isopropyl, isobutyl group, cyclohexyl are the example explanation).
Table: the asymmetric alkene hydrogenation result of alpha-substituted aromatic radical ethene:
Wherein:
| Entry | Substrate | Yield(％) | ee(％) | |
| Ar | R | |||
| 1 2 3 4 5 6 7 8 9 10 11 | Ph p-MePh m-MePh m-MeOPh p-MeOPh p-ClPh Ph Ph Ph 2-naphtyl 2-naphtyl | i-Pr i-Pr i-Pr i-Pr i-Pr i-Pr Et n-Pr i-Bu i-Pr c-C 6H 11 | 89 96 96 95 94 76 80 92 92 94 92 | 99(S) 97 98 98 98 94 70(S) 82 88 99 99 |
Claims (8)
1. a chiral spirocyclo mono-phosphorus (phosphine) part is with the metal complex catalyst that nickel forms, and the cationic moiety that it is characterized in that it comprises a Ni atom, chiral spirocyclo mono-phosphorus (phosphine) part and one and has allylic group, and its structural formula is:
Wherein: n=0～3, R
0, R
1, R
2, R
3Be C
1～C
8Alkyl, substituted alkyl (substituting group is C
1～C
8Alkoxyl, haloalkyl, and ester group), phenyl, (substituting group on the phenyl is C to substituted-phenyl
1～C
8Alkyl, alkoxyl, phenyl, substituted-phenyl, substituting group quantity is 1～5), 1-naphthyl, 2-naphthyl; Z is O, CH
2Y is NR
4R
5, OR
6, R
7, [R wherein
4, R
5, R
6, R
7Be C
1～C
8Alkyl, substituted alkyl, phenyl, substituted-phenyl (substituting group on the phenyl is C
1～C
8Alkyl, alkoxyl, phenyl, substituted-phenyl, substituting group quantity is 1～5), 1-naphthyl, 2-naphthyl]; X is halide ion, C
1～C
8Carboxylate radical, BARF
-[BARF
-Be four (3, the 5-bis trifluoromethyl phenyl) borate], four (perfluor tert-butoxy) aluminium ion, four (hexafluoro isopropoxy) aluminium ion, hexafluoro-phosphate radical, hexafluoroantimonic anion, tetrafluoroborate, TFMS root.
2. according to the described metal complex catalyst of claim 1, it is characterized in that said chiral spirocyclo mono-phosphorus (phosphine) part is left-handed chiral spirocyclo mono-phosphorus (phosphine) part, or the chiral spirocyclo mono-phosphorus of dextrorotation (phosphine) part, or the chiral spirocyclo mono-phosphorus of racemization (phosphine) part.
3. according to claim 1 or 2 described metal complex catalysts, it is characterized in that described alkyl is methyl, ethyl, n-pro-pyl, isopropyl, cyclopropyl, normal-butyl, isobutyl group, sec-butyl, the tert-butyl group, cyclobutyl, n-pentyl, isopentyl, neopentyl, sec-amyl, tertiary pentyl, cyclopenta, n-hexyl, isohesyl, new hexyl, Sec-Hexyl, uncle's hexyl, cyclohexyl, n-heptyl, different heptyl, new heptyl, Zhong Gengji, uncle's heptyl, suberyl, n-octyl, iso-octyl, new octyl group, secondary octyl, uncle's octyl group, ring octyl group.
4. according to claim 1 or 2 described metal complex catalysts, it is characterized in that described alkoxyl is a methoxyl group, ethyoxyl, positive propoxy, isopropoxy, the ring propoxyl group, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, cyclobutoxy group, n-pentyloxy, isoamoxy, neopentyl oxygen, secondary amoxy, uncle's amoxy, cyclopentyloxy, just own oxygen base, dissident's oxygen base, new own oxygen base, secondary own oxygen base, the own oxygen base of uncle, cyclohexyloxy, positive heptan the oxygen base, different heptan the oxygen base, new heptan the oxygen base, Zhong Geng oxygen base, uncle's oxygen in heptan base, ring oxygen base in heptan, n-octyloxy, different octyloxy, new octyloxy, secondary octyloxy, uncle's octyloxy, the ring octyloxy.
5. according to claim 1 or 2 described metal complex catalysts, it is characterized in that described ester group is a methoxycarbonyl group, carbethoxyl group, the third oxygen carbonyl, the different third oxygen carbonyl, butoxy carbonyl, isobutyl boc, secondary butoxy carbonyl, tertbutyloxycarbonyl, the ring butoxy carbonyl, positive penta oxygen carbonyl, isoamyl oxygen carbonyl, new penta oxygen carbonyl, secondary penta oxygen carbonyl, uncle's penta oxygen carbonyl, encircle penta oxygen carbonyl, just own oxygen carbonyl, dissident's oxygen carbonyl, new own oxygen carbonyl, secondary own oxygen carbonyl, the own oxygen carbonyl of uncle, hexamethylene oxygen carbonyl, positive heptan the oxygen carbonyl, different heptan the oxygen carbonyl, new heptan the oxygen carbonyl, Zhong Geng oxygen carbonyl, uncle's oxygen in heptan carbonyl, ring oxygen carbonyl in heptan, positive hot oxygen carbonyl, different hot oxygen carbonyl, new hot oxygen carbonyl, Zhong Xin oxygen carbonyl, the hot oxygen carbonyl of uncle, encircle hot oxygen carbonyl.
6. the chiral spirocyclo mono-phosphorus of a claim 1 (phosphine) part is with the preparation method of the metal complex catalyst of nickel formation, it is characterized in that it is at COD (COD=1 by the Ni metal precursor, the 5-cyclo-octadiene) or chiral spirocyclo mono-phosphorus (phosphine) part that adds the allyl halide of 1～2 equivalent and 1～2 equivalent in one or more solvents in the toluene, ether stir down at 0～50 ℃ and prepared in 1～10 hour, that is:
L wherein
*It is chiral spirocyclo mono-phosphorus (phosphine) part.
7. according to the described preparation method of claim 6, the catalyst that the catalyst that it is characterized in that obtaining also can obtain having different anions by anion exchange, that is:
L wherein
*It is chiral spirocyclo mono-phosphorus (phosphine) part.
8. the chiral spirocyclo mono-phosphorus of a claim 1 (phosphine) part is with the application of metal complex catalyst in asymmetry catalysis alkene hydrogenation of nickel formation, be the asymmetric alkene hydrogenation of this catalyst aromatic radical ethene and the polysubstituted ethene of aromatic radical concretely, it is characterized in that catalyst amount is 0.01～20%; Solvent is a carrene, 1, one or more in 2-dichloroethanes, toluene, the ether; Reaction temperature is-40～80 ℃; Reaction time is 1～36 hour, and its reaction equation is:
Wherein: Cat
*It is the chiral metal complex compound catalyst in the claim 1; Ar is a phenyl, (substituting group on the phenyl is C to substituted-phenyl
1～C
8Alkyl, alkoxyl, alkylthio group, haloalkyl, and amino, substituted-amino, ester group, substituting group quantity is 1～5), encircle more or heterocyclic aryl (as: 1-naphthyl, 2-naphthyl, furyl, thienyl, imidazole radicals, quinolyl, indyl), the many rings that replace or heterocyclic aryl (as: substituting group is C
1～C
8Alkoxyl, haloalkyl, 1-naphthyl, 2-naphthyl, furyl, thienyl, imidazole radicals, quinolyl, indyl that ester group replaces, substituent quantity is 1～7); R
8, R
9, R
10Be C
1～C
8Alkyl, (as: substituting group is C to the alkyl of various replacements
1～C
8Alkoxyl, alkylthio group, haloalkyl), phenyl, (substituting group on the phenyl is C to substituted-phenyl
1～C
8Alkyl, alkoxyl, ester group, substituting group quantity is 1～5), encircle more or heterocyclic aryl (as: 1-naphthyl, 2-naphthyl, furyl, thienyl, imidazole radicals, quinolyl, indyl), the many rings that replace or heterocyclic aryl (as: substituting group is C
1～C
8Alkoxyl, ester group, the 1-naphthyl of replacement, 2-naphthyl, furyl, thienyl, imidazole radicals, quinolyl, indyl, substituent quantity is 1～7); Described alkyl is methyl, ethyl, n-pro-pyl, isopropyl, cyclopropyl, normal-butyl, isobutyl group, sec-butyl, the tert-butyl group, cyclobutyl, n-pentyl, isopentyl, neopentyl, sec-amyl, tertiary pentyl, cyclopenta, n-hexyl, isohesyl, new hexyl, Sec-Hexyl, uncle's hexyl, cyclohexyl, n-heptyl, different heptyl, new heptyl, Zhong Gengji, uncle's heptyl, suberyl, n-octyl, iso-octyl, new octyl group, secondary octyl, uncle's octyl group, ring octyl group; Described alkoxyl is a methoxyl group, ethyoxyl, positive propoxy, isopropoxy, the ring propoxyl group, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, cyclobutoxy group, n-pentyloxy, isoamoxy, neopentyl oxygen, secondary amoxy, uncle's amoxy, cyclopentyloxy, just own oxygen base, dissident's oxygen base, new own oxygen base, secondary own oxygen base, the own oxygen base of uncle, cyclohexyloxy, positive heptan the oxygen base, different heptan the oxygen base, new heptan the oxygen base, Zhong Geng oxygen base, uncle's oxygen in heptan base, ring oxygen base in heptan, n-octyloxy, different octyloxy, new octyloxy, secondary octyloxy, uncle's octyloxy, ring octyloxy etc.; Described haloalkyl is the haloalkyl of fluorine-containing, chlorine, bromine, iodine; Ester group is C such as methoxycarbonyl group, carbethoxyl group, the third oxygen carbonyl, the different third oxygen carbonyl, butoxy carbonyl, isobutyl boc
1-C
8Ester group.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200510016457 CN1792452A (en) | 2005-11-29 | 2005-11-29 | Metal complex catalyst of chiral spirocyclo mono-phosphorus (phosphine) ligand and nickel, its prepn. method and application |
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|---|---|---|---|
| CN 200510016457 CN1792452A (en) | 2005-11-29 | 2005-11-29 | Metal complex catalyst of chiral spirocyclo mono-phosphorus (phosphine) ligand and nickel, its prepn. method and application |
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|---|---|---|---|
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009149564A (en) * | 2007-12-20 | 2009-07-09 | Osaka Univ | Iodide, and oxidative method for forming asymmetric spiro-ring using the same |
| CN113527066A (en) * | 2021-06-10 | 2021-10-22 | 香港科技大学深圳研究院 | Chiral spiro compound and preparation method and application thereof |
-
2005
- 2005-11-29 CN CN 200510016457 patent/CN1792452A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009149564A (en) * | 2007-12-20 | 2009-07-09 | Osaka Univ | Iodide, and oxidative method for forming asymmetric spiro-ring using the same |
| CN113527066A (en) * | 2021-06-10 | 2021-10-22 | 香港科技大学深圳研究院 | Chiral spiro compound and preparation method and application thereof |
| CN113527066B (en) * | 2021-06-10 | 2024-02-20 | 香港科技大学深圳研究院 | Chiral spiro compound and preparation method and application thereof |
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