CN105985365A - Carbene insertion method for preparing function group-containing chiral borane - Google Patents
Carbene insertion method for preparing function group-containing chiral borane Download PDFInfo
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Abstract
The invention relates to a method for preparing function group-containing chiral borane with high optical purity. The diene ligand can be used as a catalyst in the asymmetric reaction of insertion of monovalent rhodium metal carbene to the boron-hydrogen bond of an amine-boron complex or N-hetercyclic carbene-borane in order to realize the method. The method has the advantages of mild reaction conditions, simple operation, good substrate applicability, and realization of preparation of alpha-carbonyl group-containing organic borane compounds with high optical purity under high yield and high stereoselectivity.
Description
Technical field
The invention belongs to chemical field, be specifically related to the asymmetric insertion reaction structure that monovalence rhodium metal Cabbeen participates in
Build carbon-boron bond, the method for the preparation chiral borane containing-carbonyl functional group.
Background technology
In organic synthesis, it is structure that transition metal-catalyzed Cabbeen inserts C-H, X-H (X=O, N, S, Si) key
Build a very important method of class of C-C, C-X key.It is catalyzed asymmetric Cabbeen and inserts the research of c h bond
Through making great progress ((a) Davies, H.M.；Beckwith,R.E.Chem.Rev.2003,103,
2861；(b)Doyle,M.P.；Duffy,R.；Ratnikov,M.；Zhou,L.Chem.Rev.2010,110,
704.), insert X-H key based on asymmetric Cabbeen then dashing forward with the method building C-X key
Broken, Rh (II), Cu (I), Cu (II), Ir (III), Fe (II) as catalyst under suitable chiral ligand effect permissible
Realize this kind of conversion (Zhu, S.-F. smoothly；Zhou,Q.-L.Acc.Chem.Res.2012,45,1365.).Though
So monovalence rhodium catalyst can be catalyzed the most right to carbonyl, imines and electron deficiency eneyne of organoboron reagent effectively
Claim addition, but monovalence rhodium is the most considerably less for the research of metal carbene chemistry as central metal, relates to one
The asymmetric reaction phoenix feathers and unicorn horns especially that valency rhodium Cabbeen participates in, the most recent three documents relate to utilize monovalence
Rhodium Cabbeen builds new C-C key ((a) Nishimura, T.；Maeda,Y.；Hayashi,T.Angew.Chem.
Int.Ed.2010,49,7324；(b)Yada,A.；Fujita,S.；Murakami,M.J.Am.Chem.Soc.
2014,136,7217；(c)Ma,X.；Jiang,J.；Lv,S.；Yao,W.；Yang,Y.；Liu,S.；Xia,F.；
Hu,W.Angew.Chem.Int.Ed.2014,126,13352).Up till now to this end, also there is no monovalence rhodium card
The report that C-H or X-H key is inserted by guest.
Organo-borane is a very important compound of class, and it is at Organometallic Chemistry, organic synthesis, medicine
Chemistry and material science suffer from application widely.((a)Jana,R.；Pathak,T.P.；Sigman,
M.S.Chem.Rev.2011,111,1417；(b)Ollivier,C.；Renaud,P.Chem.Rev.2001,
101,3415；(c)Soloway,A.H.；Tjarks,W.；Barnum,B.A.；Rong,F.G.；Barth,R.
F.；Codogni,I.M.；Wilson,J.G.Chem.Rev.1998,98,1515；(d)Jakle,F.Chem.
Rev.2010,110,3985)。
Along with chirality the reach of science, the synthesis of chirality boron-containing compound also becomes in organic chemistry one very
Popular research field.It is true that asymmetric reduction or boronation reaction always synthesize this compounds
The most classical method ((a) .Burgess, K.；Ohlmeyer,M.J.Chem.Rev.1991,91,1179；(b)
Carroll,A.-M.；O’Sullivan,T.P.；Guiry,P.J.Adv.Syn.Cat.2005,347,609；(c)
Crudden,C.M.；Edwards,D.Eur.J.Org.Chem.2003,4695).By the boron of metal carbene
-hydrogen insertion reaction can also build this compounds, but the successful example of document is little, will realize catalysis not
Symmetrical boron-hydrogen (B-H) insertion reaction is the most difficult, only has Liang Ge seminar the most at present in 2013 respectively
Report bivalence rhodium and the catalysis of monovalence copper-diazo ester and azepine Cabbeen-borine (NHC-BH3) and nitrogen/phosphine-
Boron-hydrogen (B-H) insertion reaction ((a) Li, X. between boron complex；Curran,D.P.J.Am.Chem.Soc.
2013,135,12076；(b)Cheng,Q.-Q.；Zhu,S.-F.；Zhang,Y.-Z.；Xie,X.-L.；Zhou,
Q.-L.J.Am.Chem.Soc.2013,135,14094), Zhou group utilizes chiral spiro oxazole the most simultaneously
Quinoline part achieves the asymmetric boron of the catalysis to phosphine-boron complex-hydrogen (B-H) insertion reaction first, achieves
91-94%ee.
It may be said that the research being catalyzed asymmetric boron-hydrogen (B-H) insertion reaction is the most at the early-stage, the end of such reaction
The thing scope of application and stereo selectivity control etc. are the most preferable.The method of asymmetric synthesis of single report with
Phosphine-boron complex is as boron source, and phosphine-boron complex needs by the substituted phosphonium chloride of corresponding alkyl at tetrahydrochysene
Under the conditions of aluminum lithium, dimethyl sulphide with borine reacts and obtains, and source chemicals is expensive and prepares and is difficult to, separately
On the one hand, phosphine-boron complex property stable in the air is poor, it is difficult to meet the chemical combination efficiently preparing high-optical-purity
The demand of thing.
Therefore, this area is in the urgent need to the new highly effective of development, the asymmetric boron-hydrogen of the catalysis (B-H) of low cost
Insertion reaction method.
Summary of the invention
It is an object of the invention to provide a kind of highly effective, the asymmetric boron-hydrogen of the catalysis (B-H) of low cost is inserted
Enter reaction method.
It is a further object of the present invention to provide the chiral borane containing alpha-carbonyl functional group of a class high-optical-purity
And the application at aspects such as pharmaceutical synthesis.
In a first aspect of the present invention, it is provided that a kind of side prepared containing alpha-carbonyl chirality organo-borane compounds
Method, including step:
In organic solvent, the composition catalyst at monovalence rhodium metal catalyst and chiral diene ligand exists
Under, catalysis compound α-diazo ester shown in formulas below or ketone 1 to amine-boron complex or azepine Cabbeen-
Borine 2 carries out the asymmetric insertion reaction of boron-hydrogen bond, thus formed shown in structural formula 3 or ent-3 containing α-
Carbonyl chirality organo-borane compounds；
In formula,
Ar is unsubstituted or substituted C6-C30Aryl, wherein said replacement refer to have one or more (as
1-5) substituent group, wherein said substituent group is selected from lower group: halogen, C1-6Alkyl, C1-6Haloalkyl,
C1-6Alkoxyl, C1-6Halogenated alkoxy, benzyloxy or a combination thereof；Described halogen be F, Cl, Br or
I；
R1For C1-6Alkyl, C1-6Haloalkyl, unsubstituted or substituted C6-C30Aryl, aryl are substituted
C1-6Alkyl, C1-6Alkoxyl, C1-6The substituted C of halogenated alkoxy, aryloxy or aryl1-6Alkoxyl；
Wherein said aryl is phenyl or the phenyl that replaced by one or more substituent groups selected from lower group: halogen
Element, C1-6Alkyl, C1-6Haloalkyl, nitro；Described halogen is F, Cl, Br, I；
X is C1-24Three grades of alkyl tertiary amines or azepine Cabbeen.
In another preference, described Ar is substituted or unsubstituted phenyl, substituted or unsubstituted naphthalene
Base.
In another preference, described C1-6Haloalkyl includes monohaloalkyl, polyhalo or perhalogeno
C1-6Alkyl.
In another preference, wherein rhodium metal catalyst consumption is 0.5～30mol%；And/or chirality is double
Alkene part consumption is 0.8～30mol%；Wherein, gauge is used by compound α-diazo ester or ketone 1.
In another preference, described chiral diene ligand has a following structural formula:
Wherein, R2And R3It is each independently substituted or unsubstituted phenyl, naphthyl or other aryl, institute
The substituent group stated is selected from lower group: halogen, unsubstituted or C by one or more halogen substiuted1-6Alkyl or
Unsubstituted or C by one or more halogen substiuted1-6Alkoxyl.
In another preference, described R2And R3May be the same or different.
In another preference, described R2For unsubstituted phenyl, and R3For substituted phenyl (preferably by
One or more halogens or C1-6The substituted phenyl of haloalkyl).
In another preference, described chiral diene ligand is selected from lower group:
In another preference, described monovalence rhodium metal is selected from lower group: [Rh (C2H4)2Cl]2、
[Rh(C2H4)2OH]2、[Rh(coe)2Cl]2、[Rh(coe)2OH]]2、[Rh(C2H4)2OMe]2、[Rh(coe)2OMe]2
Or a combination thereof.
In another preference, described borane reactant 2 is the borine reaction substrate selected from lower group: C1-24's
Three grades of alkyl tertiary amine-boron complexs or azepine Cabbeen-borine.
In another preference, described method has a feature selected from lower group:
(1) organic solvent described in be C1～4 halogenated alkane (preferably dichloromethane, 1.2-dichloroethanes,
Chloroform or a combination thereof)；
(2) reaction temperature is at 15-50 DEG C；
(3) response time is 0.1-48 hour.
A second aspect of the present invention, it is provided that the compound shown in a kind of structural formula 3 or ent-3,
In formula,
Ar、X、R1As first aspect defines,
Z is O or OR5, wherein R5For H, C1-6Alkyl, C1-6Haloalkyl；
And it is when Z is O, describedFor double bond；When Z is OR5Time, describedFor list
Key.
In another preference, ee value >=90% of described formula 3 or ent-3 compound, preferably >=95%,
More preferably >=99%.
In another preference, described Ar, R1、R2、R3、R5Or the group such as Z is respectively embodiment
In group corresponding in each particular compound.
In another preference, described compound be prepared compound in embodiment (compound 3aa-3an,
3a-3z, 3za-3zc, 6aa, 6ab, 6b, 7aa, 7ab, and 7b).
In another preference, described compound is selected from lower group:
A third aspect of the present invention, it is provided that a kind of chiral diene ligand, has a following structural formula:
Wherein, R2And R3It is each independently substituted or unsubstituted phenyl, naphthyl or other aryl, institute
The substituent group stated is selected from lower group: halogen, unsubstituted or C by one or more halogen substiuted1-6Alkyl or
Unsubstituted or C by one or more halogen substiuted1-6Alkoxyl；
And R2And R3It is different.
In another preference, described R2For unsubstituted phenyl, and R3For substituted phenyl.
In another preference, described R3For by one or more halogens or C1-6Haloalkyl is replaced
Phenyl.
In another preference, described chiral diene ligand is selected from lower group:
In should be understood that within the scope of the present invention, above-mentioned each technical characteristic of the present invention and below (as implemented
Example) in can be combined with each other between each technical characteristic of specifically describing, thus constitute new or preferred technology
Scheme.As space is limited, the most tired at this state.
Detailed description of the invention
The present inventor is through extensively in-depth study, first it was unexpectedly observed that utilize rhodium (I)/chiral diene to join
Compound is as catalyst, by monovalence rhodium metal Cabbeen to amine-boron complex or the boron-hydrogen of azepine Cabbeen-borine
The asymmetric insertion reaction of key, can efficiently prepare have high-optical-purity containing alpha-carbonyl organic boron alkanes
Compound.Additionally, by the chiral ligand selecting various configuration, it is contrary that the inventive method can obtain configuration
Containing alpha-carbonyl chiral borane.Complete the present invention on this basis.
Term
As used herein, the straight or branched alkyl of C1-C10 pointed out in term " alkyl ", in the present invention,
Alkyl also includes that the one or more H on alkyl are selected from the substituted group of substituent group of lower group: halogen,
Substituted or unsubstituted phenyl, unsubstituted or C by one or more halogen substiuted1-6Alkyl.Should be understood that
This term also includes the substituted or unsubstituted cycloalkyl of C3-10.
As used herein, the alkoxyl of the straight or branched of C1-C10 pointed out in term " alkoxyl ", at this
In invention, alkoxyl also includes that the one or more H on alkyl are selected from the substituted base of substituent group of lower group
Group: halogen, substituted or unsubstituted phenyl, unsubstituted or C by one or more halogen substiuted1-6Alkane
Base.
As used herein, term " aryl " or " Ar " point out C6-C30Aryl, representational example is benzene
Base, naphthyl, anthryl, phenanthryl.In the present invention, aryl also includes that the one or more H on aryl are selected
The substituted group of substituent group from lower group: halogen, phenyl, unsubstituted or taken by one or more halogens
The C in generation1-6Alkyl, unsubstituted or C by one or more halogen substiuted1-6Alkoxyl.
As used herein, term " one or more " is often referred to 1-6, preferably 1-5, more preferably
1-3.
As used herein, term " Ph " represents phenyl.
As used herein, term " rt " expression room temperature, such as 10-50 DEG C.
Preparation method
The synthetic method of the present invention can be represented by following type reaction formula:
Reaction substrate 1 is-diazo ester or ketone, and wherein, Ar is unsubstituted or substituted C6-C30Aryl (as
Substituted or unsubstituted phenyl, naphthyl or other aryl), wherein said replacement refer to have one or more (as
1-5) substituent group, wherein said substituent group is selected from lower group: halogen, C1-6Alkyl, C1-6Haloalkyl,
C1-6Alkoxyl, C1-6Halogenated alkoxy, benzyloxy or a combination thereof；Described halogen be F, Cl, Br or
I；
R1For C1-6Alkyl, C1-6Haloalkyl, unsubstituted or substituted C6-C30Aryl, aryl are substituted
C1-6Alkyl, C1-6Alkoxyl, C1-6The substituted C of halogenated alkoxy, aryloxy or aryl1-6Alkoxyl；
Wherein said aryl is phenyl or the phenyl that replaced by one or more substituent groups selected from lower group: halogen
Element, C1-6Alkyl, C1-6Haloalkyl, nitro；Described halogen is F, Cl, Br, I；
In reaction substrate 2, X is C1-24Three grades of alkyl tertiary amines or azepine Cabbeen；
[Rh (I)] refers to that monovalence rhodium metal catalyst, representational example include (but being not limited to):
[Rh(C2H4)2Cl]2、[Rh(C2H4)2OH]2、[Rh(coe)2Cl]2、[Rh(coe)2OH]2、
[Rh(C2H4)2OMe]2；[Rh(coe)2OMe]2, or a combination thereof.
In the present invention, representational chiral diene ligand has a following structural formula:
Wherein, R2And R3It is each independently substituted or unsubstituted phenyl, naphthyl or other aryl, institute
The substituent group stated is selected from lower group: halogen, unsubstituted or C by one or more halogen substiuted1-6Alkyl or
Unsubstituted or C by one or more halogen substiuted1-6Alkoxyl.
In the present invention, R2And R3Can be identical or different.
In another preference, described R2For unsubstituted phenyl, and R3For substituted phenyl (preferably by
One or more halogens or C1-6The substituted phenyl of haloalkyl).
In the present invention, the structural formula of the typical compound of chiral diene ligand includes (but being not limited to):
In the present invention, described solvent is conventional organic solvent, can be the halogenated alkane such as two of C1～4
Chloromethanes, 1.2-dichloroethanes, chloroform or a combination thereof.
In the above-mentioned reaction method of the present invention, reaction temperature is not particularly limited, and is usually-80 DEG C to the temperature that refluxes
Degree, is more preferably 0-30 DEG C by preferably 0-50 DEG C.
In the above-mentioned reaction method of the present invention, the response time is not particularly limited, usually 0.1-48 hour,
Preferably 0.5-24 hour.
In a preference of the present invention, representational synthetic method can be described as follows:
In the presence of an organic, by monovalence rhodium catalyst and chiral diene ligand complexation reaction at room temperature
10-30 minute, add reaction substrate 1 and 2 and continue reaction 1-10 hour, it is possible to obtain the present invention
Described high-optical-purity is containing-carbonyl organo-borane compounds.In the reaction, reaction substrate 1 and 2
Mol ratio be (1-3): 1, preferably 1.5:1；Rhodium metal catalyst consumption is 0.5～30mol%, preferably
3mol%；Chiral diene ligand consumption is 0.8～30mol%, preferably 3.3mol%；Reaction temperature is 15-50
DEG C, preferably room temperature (25 DEG C)；The preferred dichloromethane of reaction dissolvent.
High-optical-purity containing-carbonyl organo-borane compounds
By the method for the present invention, that can efficiently prepare high-optical-purity contains-carbonyl organic boron alkanes chemical combination
Thing.
In the present invention, some representational organo-borane compounds containing alpha-carbonyl are listed in Tables 1 and 2.
With monovalence rhodium catalyst [Rh (C2H4)2Cl]2, as a example by chiral diene ligand (R, R)-4e, with α-diazo ester
Respectively amine-boron complex 5 is carried out asymmetric boron-hydrogen insertion reaction with α-diazo-ketones substrate 1, can efficiently make
Required product, yield (yield) is good, and enantioselectivity (ee) is outstanding, the highest can reach 99%.
Asymmetric boron-the hydrogen of amine-boron complex 5 is inserted by table 1. monovalence rhodium catalysis α-diazonium tert-butyl ester
| Numbering | 1 | Ar | 3 | Productivity (%) | Ee (%) |
| 1 | 1a | Ph | 3a | 92 | 99 |
| 2 | 1b | 4-FC6H4 | 3b | 86 | 99 |
| 3 | 1c | 4-ClC6H4 | 3c | 87 | 99 |
| 4 | 1d | 4-MeC6H4 | 3d | 96 | 98 |
| 5 | 1e | 2-naphthyl | 3e | 87 | 99 |
| 6 | 1f | 3-CF3C6H4 | 3f | 84 | 97 |
| 7 | 1g | 3,5-Me2C6H4 | 3g | 80 | 98 |
| 8 | 1h | 3-BrC6H4 | 3h | 83 | 98 |
| 9 | 1i | 3-MeC6H4 | 3i | 82 | 98 |
| 10 | 1j | 4-MeOC6H4 | 3j | 82 | 97 |
| 11 | 1k | 2-MeC6H4 | 3k | 75 | 97 |
| 12 | 1l | 2-FC6H4 | 3l | 80 | 96 |
Asymmetric boron-the hydrogen of amine-boron complex 5 is inserted by table 2. monovalence rhodium catalysis α-diazo-ketones.
| Numbering | 1 | Ar | R1 | 3 | Productivity (%) | Ee (%) |
| 1 | 1m | Ph | Ph | 3m | 76 | 97 |
| 2 | 1n | 2-naphthyl | Ph | 3n | 67 | 96 |
| 3 | 1o | 3-BrC6H4 | Ph | 3o | 69 | 96 |
| 4 | 1p | 4-ClC6H4 | Ph | 3p | 64 | 96 |
| 5 | 1q | 4-MeC6H4 | Ph | 3q | 65 | 95 |
| 6 | 1r | Ph | 4-FC6H4 | 3r | 73 | 96 |
| 7 | 1s | Ph | 4-ClC6H4 | 3s | 68 | 97 |
| 8 | 1t | Ph | 4-MeOC6H4 | 3t | 85 | 97 |
| 9 | 1u | Ph | 2-MeC6H4 | 3u | 48 | 95 |
| 10 | 1v | ph | 3-FC6H4 | 3v | 71 | 96 |
| 11 | 1w | 3-BrC6H4 | 4-MeC6H4 | 3w | 70 | 98 |
| 12 | 1x | Ph | Et | 3x | 73 | 94 |
| 13 | 1y | Ph | Bu | 3y | 73 | 95 |
| 14 | 1z | Ph | i-Pr | 3z | 54 | 93 |
Application
Present invention also offers the application containing alpha-carbonyl organo-borane compounds of the present invention, especially in preparation
There is the application in terms of the medicinal intermediate of high-optical-purity or reactive compound.
In the present invention, a kind of representational purposes is as follows:
In this application, the organo-borane compounds containing alpha-carbonyl of the present invention is reduced, thus is formed
Compound 6a or 6b of hydroxyl, these compounds 6a or 6b is converted into useful intermediate 7a subsequently
Or 7b.
Another kind of representational purposes is as follows:
Above-mentioned various in, Ar, Ar1, Ar2It is defined as above, represents phenyl, naphthyl or other aryl.
In another preference, representational purposes is as follows:
By the product (-78 DEG C) at low temperatures obtained by α-diazo-ketones insertion B-H key through DIBAL-H process,
Obtaining corresponding chiral alcohol, product absolute configuration is determined by single crystal diffraction；Chiral alcohol product is at pinacol
Reason, forms corresponding adjacent hydroxyl pinacol borine.
Main advantages of the present invention include:
(a) using monovalence rhodium as catalyst, by simple and easy to get and that chemical stability is good amine-boron complex or nitrogen
Miscellaneous Cabbeen-borine is as boron source；
B () is under chiral diene ligand effect, it is achieved that the asymmetric boron-hydrogen bond of the catalysis of Cabbeen mediation inserts
Reaction, for preparing the various chiral borane containing alpha-carbonyl functional group.
(c) the inventive method good substrate applicability.
(d) the inventive method reaction gentleness, easy and simple to handle；
E the stereo selectivity of the product of () present invention is high, have prospects for commercial application.
Below in conjunction with specific embodiment, the present invention is expanded on further.Should be understood that these embodiments are only used for
The bright present invention rather than restriction the scope of the present invention.The experiment side of unreceipted actual conditions in the following example
Method, generally according to normal condition, or according to the condition proposed by manufacturer.Unless otherwise indicated, otherwise
Percentage ratio and number are percentage by weight and parts by weight.
Embodiment 1
The synthesis of compound 3aa:
By [Rh (C2H4)2Cl]2(0.0015mmol, 1.5mol%), diene ligand (R, R)-4a puts into reaction
In Ping, after anhydrous and oxygen-free processes, add dichloromethane (1mL), at room temperature stirring reaction 30min；Past
System adds diazonium substrateWith amine-boron complex 5, continue reaction.TLC monitoring reaction is completely
Afterwards, it is spin-dried for reactant liquor, with silica gel column chromatography isolated product 3aa, for white solid, 98% productivity,
60%ee.
3aa 1H NMR(300MHz,CDCl3) δ 7.44 (d, J=7.5Hz, 2H),
7.33-7.19 (m, 2H), 7.10 (t, J=7.5Hz, 1H), 3.62 (s, 3H), 3.33-2.25 (m, 1H),
3.20-3.10(m,1H),3.00-2.90(m,1H),2.88-2.77(m,1H),2.60-2.49(m,4H),
2.10-1.76(m,5H).
Embodiment 2
The synthesis of compound 3ab:
Amine-boron complex raw material used in embodiment 1 is changed toRemaining experimental implementation is with implementing
Example 1.Obtain product 3ab, for white solid, 90% productivity, 60%ee.
3ab 1H NMR(300MHz,CDCl3) δ 7.41 (t, J=7.2Hz, 2H),
7.25-7.19 (m, 2H), 7.08 (t, J=7.2Hz, 1H), 3.60 (s, 3H), 3.13 (s, 1H), 2.86-2.62 (m,
6H),1.17-0.96(m,9H).
Embodiment 3
The synthesis of compound 3ac:
Amine-boron complex raw material used in embodiment 1 is changed toRemaining experimental implementation is with real
Execute example 1.Obtain product 3ac, for white solid, 83% productivity, 66%ee.
3ac 1H NMR(300MHz,CDCl3) δ 7.43 (d, J=7.2Hz, 2H),
7.35-7.16 (m, 3H), 7.08 (t, J=7.2Hz, 1H), 3.60 (s, 3H), 3.12 (s, 1H), 2.56 (m, 6H),
1.48 (m, 6H), 1.23-1.04 (m, 6H), 0.88 (t, J=7.2Hz, 9H).
Embodiment 4
The synthesis of compound 3ad:
Have only to be changed to amine-boron complex raw material used in embodiment 1Remaining experimental implementation is joined
Examine embodiment 1.Obtain product 3ad, for white solid, 52% productivity, 66%ee.
3ad 1H NMR(300MHz,CDCl3) δ 7.27-7.22 (m, 2H), 7.13 (t, J=
7.6Hz, 2H), 7.03 (d, J=7.6Hz, 1H), 6.76 (s, 2H), 3.61 (s, 3H), 3.45 (s, 6H), 3.28
(s,1H).
Embodiment 5
The synthesis of compound 3ae:
Amine-boron complex raw material used in embodiment 1 is changed toRemaining experimental implementation is with real
Execute example 1.Obtain product 3ae, for white solid, 40% productivity, 64%ee.
Embodiment 6
The synthesis of compound 3af:
Diazonium substrate used in embodiment 1 is changed toRemaining experimental implementation, with embodiment 1, obtains
To product 3af, for white solid, yield: 92% productivity, 81%ee.
(m,4H),2.12-1.75(m,5H),1.32-1.15(m,3H).
Embodiment 7
The synthesis of compound 3ag:
Diazonium substrate used in embodiment 1 is changed toRemaining experimental implementation, with embodiment 1, obtains
Product 3ag, for white solid；94% productivity, 93%ee.
2.65-2.47 (m, 4H), 2.12-1.70 (m, 6H), 1.20 (dd, J=6.2,2.3Hz, 6H).
Embodiment 8
The synthesis of compound 3ah:
Diazonium substrate used in embodiment 1 is changed toRemaining experimental implementation, with embodiment 1, obtains
Product 3ah, for white solid；92% productivity, 95%ee.
(m,5H).
Embodiment 9
The synthesis of compound 3ai:
By [Rh (C2H4)2Cl]2(0.0015mmol, 1.5mol%), diene ligand (R, R)-4a puts into reaction
In Ping, after anhydrous and oxygen-free processes, add dichloromethane (1mL), react 30min at room temperature；Toward system
Middle additionWithContinue reaction, after TLC monitoring reaction completely, be spin-dried for reactant liquor, use
Silica gel column chromatography isolated product 3ai, for white solid, 83% productivity, 93%ee.
Embodiment 10
The synthesis of compound 3aj:
Amine-boron complex used in embodiment 9 is changed toRemaining experimental implementation with embodiment 9,
For white solid, 80% productivity, 95%ee.
3aj 1H NMR(300MHz,CDCl3) δ 7.51 (d, J=7.4Hz, 2H),
Embodiment 11
The synthesis of compound 3ak:
Diazonium substrate used in embodiment 1 is changed toRemaining experimental implementation, with embodiment 1, obtains
To product 3ak, for white solid；68% productivity, 91%ee.
3ak 1H NMR(300MHz,CDCl3)δ8.09-7.91(m,1H),
4H).
Embodiment 12
The synthesis of compound 3al:
Diazonium substrate used in embodiment 1 is changed toRemaining experimental implementation, with embodiment 1, obtains
To product 3al, for white solid；78% productivity, 94%ee.
3al 1H NMR(300MHz,CDCl3)δ7.95-7.66(m,3H),
2.50-2.26(s,2H),2.05-1.82(m,4H).
Embodiment 13
The synthesis of compound 3am:
Diazonium substrate used in embodiment 1 is changed toRemaining experimental implementation with embodiment 1,
Obtain product 3am, for white solid；95% productivity, 95%ee.
2.10-1.75(m,5H).
Embodiment 14
The synthesis of compound 3an:
Diazonium substrate used in embodiment 1 is changed toRemaining experimental implementation with embodiment 1,
Obtain product 3an, for white solid；90% productivity, 89%ee.
Embodiment 15
The synthesis of compound (R)-3a:
Experiment one: by [Rh (C2H4)2Cl]2(0.0015mmol, 1.5mol%), diene ligand (R, R)-4a throws
Enter in reaction bulb, after anhydrous and oxygen-free processes, add dichloromethane (1mL), react 30min at room temperature；
In system, add 1a and 5 continue reaction, after TLC monitoring reaction completely, be spin-dried for reactant liquor, use silicon
Plastic column chromatography isolated product (R)-3a, for white solid, 70% productivity, 97%ee.
Experiment two: will test part (R, R)-4a used in and change (R, R)-4b into, remaining experimental implementation is with real
Test one, obtain product (R)-3a, for white solid, 44% productivity, 93%ee.
Experiment three: will test part (R, R)-4a used in and change (R, R)-4c into, remaining experimental implementation is with real
Test one, obtain product (R)-3a, for white solid, 78% productivity, 94%ee.
Experiment four: will test part (R, R)-4a used in and change (R, R)-4d into, remaining experimental implementation is same
Experiment one, obtains product (R)-3a, for white solid, 93% productivity, 98%ee.
Experiment five: will test part (R, R)-4a used in and change (R, R)-4e into, remaining experimental implementation is with real
Test one, obtain product (R)-3a, for white solid, 92% productivity, 99%ee.
Experiment six: will test part (R, R)-4a used in and change (R, R)-4h into, remaining experimental implementation is with real
Test one, obtain product (R)-3a, for white solid, 73% productivity, 97%ee.
13C NMR(101MHz,CDCl3)δ178.0,144.8,129.3,127.7,124.6,78.6,61.7,61.7,
(47.9,28.4,22.5,22.3.ESI-MS m/z, %) 312 [M+Na]+.
Embodiment 16
The synthesis of compound (S)-3a:
Change part (R, R)-4a used in embodiment 15 into (S, S)-4a, the same experiment one of remaining experimental implementation,
Obtain product (S)-3a, for white solid, 67% productivity, 96%ee.
(m,1H),2.57(s,3H),2.15-1.70(m,6H),1.42(s,9H).
Embodiment 17
By [Rh (C2H4)2Cl]2(0.0015mmol, 1.5mol%), diene ligand (R, R)-4e puts into reaction
In Ping, after anhydrous and oxygen-free processes, add dichloromethane (1mL), react 30min at room temperature；Toward system
Middle addition 1b and 5 continues reaction, reacts at room temperature, after TLC monitoring reaction completely, is spin-dried for reaction
Liquid, with silica gel column chromatography isolated product 3b, for white solid, 86% productivity, 99%ee.
3b 1H NMR(300MHz,CDCl3) δ 7.34 (t, J=8.7Hz, 2H),
178.0,160.7(d,JC-F=240.0Hz), 140.4,130.5 (d, JC-F=7.4Hz), 114.3 (d, JC-F=
21.3Hz), 78.8,61.8,61.7,48.0,28.4,22.5,22.4.ESI-MS (m/z, %) 330 [M+Na]+.
Embodiment 18
Diazonium substrate used in embodiment 17 is changed to 1c, and remaining experimental implementation, with embodiment 17, is produced
Thing 3c, for white solid；87% productivity, 99%ee.
δ177.6,143.4,130.6,130.2,127.8,78.9,61.8,61.7,48.0,28.4,22.5,22.4.
ESI-MS (m/z, %) 346 [M+Na]+.
Embodiment 19
Diazonium substrate used in embodiment 17 is changed to 1d, and remaining experimental implementation, with embodiment 17, is produced
Thing 3d, for white solid；96% productivity, 98%ee.
178.2,141.6,133.8,129.2,128.5,78.5,61.7,47.9,28.4,22.5,22.4,21.1.ESI-MS
(m/z, %) 326 [M+Na]+.
Embodiment 20
Diazonium substrate used in embodiment 17 is changed to 1e, and remaining experimental implementation, with embodiment 17, is produced
Thing 3e, for white solid；87% productivity, 99%ee.
142.7,133.7,131.8,129.4,127.6,127.0,126.5,125.3,124.5,78.8,61.80,61.77,
(48.0,28.5,22.6,22.4.ESI-MS m/z, %) 362 [M+Na]+.
Embodiment 21
Diazonium substrate used in embodiment 17 is changed to 1f, and remaining experimental implementation, with embodiment 17, is produced
Thing 3f, for white solid；84% productivity, 97%ee.
132.7,129.7(d,JC-F=32.3Hz), 127.9,126.0 (d, JC-F=3.8Hz), 123.4,121.4,79.1,
(61.9,61.7,48.0,28.3,22.45,22.43.ESI-MS m/z, %) 380 [M+Na]+.
Embodiment 22
Diazonium substrate used in embodiment 17 is changed to 1g, and remaining experimental implementation, with embodiment 17, is produced
Thing 3g, for white solid；80% productivity, 98%ee.
3g 1H NMR(300MHz,CDCl3)δ7.02(s,2H),6.72(s,1H),
340[M+Na]+.
Embodiment 23
Diazonium substrate used in embodiment 17 is changed to 1h, and remaining experimental implementation, with embodiment 17, is produced
Thing 3h, for white solid；83% productivity, 98%ee.
1H),2.62-2.55(m,1H),2.54(s,3H),2.04-1.87(m,5H),1.42(s,9H).13C NMR
(126MHz,CDCl3)δ177.4,147.4,132.2,129.2,128.0,127.6,121.8,79.0,61.8,
(61.7,48.0,28.4,22.5,22.4.ESI-MS m/z, %) 390 [M+Na]+.
Embodiment 24
Diazonium substrate used in embodiment 17 is changed to 1i, and remaining experimental implementation, with embodiment 17, is produced
Thing 3i, for white solid；82% productivity, 98%ee.
2.66-2.59(m,1H),2.58(s,3H),2.34(s,3H),2.16-1.86(m,5H),1.41(s,9H).13C
NMR(126 MHz,CDCl3)δ178.1,144.7,137.0,130.1,127.6,126.4,125.4,78.5,
(61.72,61.70,48.0,28.4,22.5,22.4,21.7.ESI-MS m/z, %) 304 [M+H]+.
Embodiment 25
Diazonium substrate used in embodiment 17 is changed to 1j, and remaining experimental implementation, with embodiment 17, is produced
Thing 3j, for white solid；82% productivity, 97%ee.
CDCl3)δ178.3,157.0,136.9,130.1,113.2,78.5,61.73,61.69,55.3,47.9,28.4,
22.5,22.3.ESI-MS (m/z, %) 342 [M+Na]+.
Embodiment 26
Diazonium substrate used in embodiment 17 is changed to 1k, and remaining experimental implementation, with embodiment 17, is produced
Thing 3k, for white solid；75% productivity, 97%ee.
3k 1H NMR (300MHz, CDCl3) δ 7.70 (d, J=7.6Hz, 1H), 7.11
(d, J=7.6Hz, 1H), 7.06 (d, J=7.2Hz, 1H), 7.00 (d, J=7.2Hz, 1H), 3.32-3.22 (m,
2H),3.16-3.07(m,1H),2.89-2.73(m,1H),2.69-2.59(m,1H),2.58(s,3H),2.34(s,
3H),2.18-1.79(m,5H),1.41(s,9H).13C NMR(126MHz,CDCl3)δ178.2,142.4,
134.6,130.1,129.4,125.5,124.4,78.4,61.8,61.5,48.0,28.3,22.5,22.4,20.6.
ESI-MS (m/z, %) 326 [M+Na]+.
Embodiment 27
Diazonium substrate used in embodiment 17 is changed to 1l, and remaining experimental implementation, with embodiment 17, is produced
Thing 3l, for white solid；80% productivity, 96%ee.
δ177.3,159.6(d,JC-F=239.4Hz), 132.2 (d, JC-F=4.3Hz), 131.7 (d, JC-F=14.2
Hz),125.6(d,JC-F=8.2Hz), 123.7 (d, J=3.1Hz), 114.1 (d, JC-F=23.9Hz), 78.8,
(61.7,61.5,48.0,28.4,22.6,22.5.ESI-MS m/z, %) 330 [M+Na]+.
Embodiment 28
Diazonium substrate used in embodiment 17 is changed to 1m, and remaining experimental implementation, with embodiment 17, obtains
Product 3m, for faint yellow solid；76% productivity, 97%ee.
2.88-2.69(m,2H),2.47(s,3H),2.41-2.30(m,4H),2.04-1.66(m,
5H).13C NMR(126MHz,CDCl3)δ203.1,144.0,139.5,131.4,129.8,128.3,128.2,
(127.9,124.9,62.3,61.5,52.2,47.7,22.5,21.8.ESI-MS m/z, %) 294 [M+H]+.
Embodiment 29
Diazonium substrate used in embodiment 17 is changed to 1n, and remaining experimental implementation, with embodiment 17, is produced
Thing 3n, for faint yellow solid；67% productivity, 96%ee.
(s,3H),2.40-2.34(m,1H),1.88-1.65(m,5H).13C NMR(101MHz,CDCl3)δ
203.2,142.0,139.5,133.7,131.9,131.5,129.6,128.4,128.2,127.6,127.1,127.0,
(125.4,124.6,62.4,61.7,52.4,47.7,22.5,21.8.ESI-MS m/z, %) 344 [M+H]+.
Embodiment 30
Diazonium substrate used in embodiment 17 is changed to 1o, and remaining experimental implementation, with embodiment 17, is produced
Thing 3o, for faint yellow solid；69% productivity, 96%ee.
CDCl3)δ202.2,146.6,139.1,132.5,131.6,129.3,128.5,128.20,128.17,127.9,
121.9,62.2,61.6,51.8,47.6,22.4,21.7.ESI-MS (m/z, %) 372 [M+H]+.
Embodiment 31
Diazonium substrate used in embodiment 17 is changed to 1p, and remaining experimental implementation, with embodiment 17, is produced
Thing 3p, for white solid；64% productivity, 96%ee.
139.2,131.6,131.1,130.5,128.3,127.9,62.3,61.7,51.4,47.7,22.5,21.8.ESI-MS
(m/z, %) 328 [M+H]+.
Embodiment 32
Diazonium substrate used in embodiment 17 is changed to 1q, and remaining experimental implementation, with embodiment 17, is produced
Thing 3q, for white solid；65% productivity, 95%ee.
140.7,139.6,134.2,131.3,129.7,128.6,128.3,128.1,62.3,61.6,51.8,47.7,22.5,
21.9,21.1.ESI-MS (m/z, %) 308 [M+H]+.
Embodiment 33
Diazonium substrate used in embodiment 17 is changed to 1r, and remaining experimental implementation, with embodiment 17, is produced
Thing 3r, for white solid；73% productivity, 96%ee.
2H),2.47(s,3H),2.40-2.34(m,2H),2.08-1.55(m,6H).13C
NMR(126MHz,CDCl3)δ201.5,164.8(d,JC-F=252.0HZ), 143.7,135.6,130.8
(d,JC-F=8.9Hz), 129.8,127.9,125.0,115.0 (d, JC-F=21.5Hz), 62.3,61.5,52.2,
(47.6,22.4,21.8.ESI-MS m/z, %) 312 [M+H]+.
Embodiment 34
Diazonium substrate used in embodiment 17 is changed to 1s, and remaining experimental implementation, with embodiment 17, is produced
Thing 3s, for white solid；68% productivity, 97%ee.
3.13-3.08(m,1H),2.86–2.72(m,2H),2.45(s,3H),2.45-2.32(m,1H),1.97-1.79
(m,4H).13C NMR(126MHz,CDCl3)δ201.3,142.9,137.2,137.0,129.2,127.9,
(127.4,124.5,61.8,61.0,47.0,45.3,21.9,21.2.ESI-MS m/z, %) 328 [M+H]+.
Embodiment 35
Diazonium substrate used in embodiment 17 is changed to 1t, and remaining experimental implementation, with embodiment 17, is produced
Thing 3t, for faint yellow solid；85% productivity, 97%ee.
2.51(s,3H),2.47-2.36(m,1H),2.14-1.69(m,5H).13C NMR(126MHz,CDCl3)δ
202.0,162.3,144.2,132.2,130.5,129.8,127.9,124.8,113.3,62.3,61.6,55.5,47.6,
22.5,21.9.ESI-MS (m/z, %) 324 [M+H]+.
Embodiment 36
Diazonium substrate used in embodiment 17 is changed to 1u, and remaining experimental implementation, with embodiment 17, is produced
Thing 3u, for faint yellow solid；48% productivity, 95%ee.
129.7,129.1,127.9,126.8,125.0,124.9,62.1,61.6,59.8,47.8,22.5,21.9,20.5.
ESI-MS (m/z, %) 308 [M+H]+.
Embodiment 37
Diazonium substrate used in embodiment 17 is changed to 1v, and remaining experimental implementation, with embodiment 17, is produced
Thing 3v, for faint yellow solid；71% productivity, 96%ee.
1H),3.16-3.07(m,1H),2.92-2.69(m,2H),2.47(s,3H),
2.40-2.32(m,1H),2.04-1.63(m,5H).13C NMR(126MHz,CDCl3)δ201.4,162.7
(d,JC-F=245.0Hz), 143.4,141.8 (d, JC-F=5.8Hz), 129.7,129.6 (d, JC-F=8.8Hz),
127.8,125.0,123.8(d,JC-F=2.6Hz), 118.1 (d, JC-F=21.4Hz), 115.0 (d, JC-F=
21.3Hz), 62.3,61.5,52.5,47.5,22.4,21.7.ESI-MS (m/z, %) 334 [M+Na]+.
Embodiment 38
Diazonium substrate used in embodiment 17 is changed to 1w, and remaining experimental implementation, with embodiment 17, is produced
Thing 3w, for faint yellow solid；70% productivity, 98%ee.
(126MHz,CDCl3)δ202.0,146.8,142.1,136.5,132.5,129.3,129.0,128.5,128.4,
(127.9,121.9,62.3,61.7,51.6,47.7,22.4,21.9,21.6.ESI-MS m/z, %) 408
[M+Na]+.
Embodiment 39
Diazonium substrate used in embodiment 17 is changed to 1x, and remaining experimental implementation, with embodiment 17, is produced
Thing 3x, for colorless oil；73% productivity, 94%ee.
214.6,144.0,129.7,127.9,124.9,62.1,61.7,47.9,34.5,22.5,22.1,8.7.ESI-MS
(m/z, %) 268 [M+Na]+.
Embodiment 40
Diazonium substrate used in embodiment 17 is changed to 1y, and remaining experimental implementation, with embodiment 17, is produced
Thing 3y, for colorless oil；73% productivity, 95%ee.
2.07-1.70(m,6H),1.51-1.43(m,2H),1.30-1.22(m,2H),0.85(t,
J=7.3Hz, 3H).13C NMR(126MHz,CDCl3)δ214.1,143.9,129.7,127.9,124.9,
(62.1,61.7,47.8,41.4,26.7,22.6,22.4,22.1,14.1.ESI-MS m/z, %) 274 [M+H]+.
Embodiment 41
Diazonium substrate used in embodiment 17 is changed to 1z, and remaining experimental implementation, with embodiment 17, is produced
Thing 3z, for colorless oil；54% productivity, 93%ee.
MHz,CDCl3)δ216.2,144.1,129.5,127.8,124.7,62.2,61.6,47.9,40.0,22.5,22.0,
20.0,18.5.ESI-MS (m/z, %) 282 [M+Na]+.
Embodiment 42
The synthesis of compound 3za:
Diazonium substrate used in embodiment 17 is changed toRemaining experimental implementation, with embodiment 17, obtains
To product 3za, for faint yellow solid；86% productivity, 83%ee.
1.99-1.75 (m, 5H) .ESI-MS (m/z, %) 254 [M+Na]+.
Embodiment 43
The synthesis of compound 3zb:
Diazonium substrate used in embodiment 17 is changed toRemaining experimental implementation with embodiment 17,
Obtain product 3zb, for faint yellow solid；71% productivity, 86%ee.
(m, 4H), 2.03-1.79 (m, 5H) .ESI-MS (m/z, %) 344 [M+Na]+.
Embodiment 44
The synthesis of compound 3zc:
Diazonium substrate used in embodiment 17 is changed toThe same embodiment of remaining experimental implementation
17, obtain product 3zc, for faint yellow solid；55% productivity, 90%ee.
(m, 5H) .ESI-MS (m/z, %) 384 [M+Na]+.
Embodiment 45
The synthesis of compound 6aa:
(R)-3m (146.5mg, 0.5mmol) is placed in reaction bulb, after anhydrous and oxygen-free processes, adds anti-
Answer solvent, after being cooled to-78 DEG C, be charged with DIBAL-H (1M in toluene, 1.5mL, 3equiv).
Keep continuing cancellation reaction system after reaction 1h at this temperature, be extracted with ethyl acetate, be dried, be spin-dried for
Product is obtained by column chromatography for separation.Obtain product 6aa, for white solid, 90% productivity, 96%ee.
6aa 1H NMR(300MHz,CDCl3)δ7.37–6.87(m,10H),4.76(d,
J=7.5Hz, 1H), 3.53 (s, 1H), 3.16 (s, 1H), 2.77 (s, 2H), 2.50-2.20 (m, 6H), 1.85 (s,
5H) .ESI-MS (m/z, %) 318 [M+Na]+.
Embodiment 46:
The synthesis of compound 6b:
Raw materials used (R)-3m in embodiment 45 is changed to (S)-3m, and remaining experimental implementation is with embodiment 45.
Obtain product 6b, for white solid, 88% productivity, 96%ee.
Embodiment 47:
The synthesis of compound 6ab:
Raw materials used (R)-3m in embodiment 45 is changed to (R)-3o, and remaining experimental implementation is with embodiment 45.
Obtain product 6ab, for white solid, 89% productivity, 95%ee.
Embodiment 48:
The synthesis of compound 7aa:
(R)-6aa, pinacol mixing are placed in reaction bulb, after anhydrous and oxygen-free processes, are charged with
Toluene, is warming up under 100 degree react 2h, TLC monitoring and is spin-dried for reaction system after completion of the reaction, use silica gel
Column chromatography obtains product.Obtain product 7aa, for colorless oil, 68% productivity, 96%ee.
Embodiment 49:
The synthesis of compound 7b:
6aa raw materials used in embodiment 48 is changed to 6b, and remaining experimental implementation is with embodiment 48.Obtain
Product 7b, for white solid, 68% productivity, 96%ee.
Embodiment 50:
The synthesis of compound 7ab:
6aa raw materials used in embodiment 48 is changed to 6ab, and remaining experimental implementation is with embodiment 48.?
To product 7ab, for white solid, 70% productivity, 95%ee.
Embodiment 51
The synthesis of compound 9:
(R)-3m (145mg, 0.5mmol) is placed in reaction bulb, after anhydrous and oxygen-free processes, adds reaction
Solvent, is charged with DIBAL-H (1M in toluene, 1.5mL, 3equiv) after being cooled to-78 DEG C.
Being warmed to room temperature reaction, TLC monitoring raw material is wholly absent rear cancellation reaction system, is extracted with ethyl acetate, does
Dry, be spin-dried for obtaining crude product.Be dissolved in THF, be charged with under ice bath DIPEA (323mg,
2.5mmol), MOMCl (161mg, 2mmol), system reacts 20h at room temperature.It is spin-dried for solvent rear pillar
Chromatograph to obtain product 8.By 8 (99mg, 0.375mmol), pinacol (442.5mg, 3.75mmol) is in through Ar
It is charged with toluene, system back flow reaction 5h after process, is spin-dried for solvent subsequently, is produced through column chromatography
Thing 9 is colorless oil, 64% productivity, 98%ee.
The all documents mentioned in the present invention are incorporated as reference the most in this application, just as each document
It is individually recited as with reference to like that.In addition, it is to be understood that after the above-mentioned teachings having read the present invention,
The present invention can be made various changes or modifications by those skilled in the art, and these equivalent form of values fall within this Shen equally
Please appended claims limited range.
Claims (10)
1. the method prepared containing alpha-carbonyl chirality organo-borane compounds, it is characterised in that include step:
In organic solvent, in the presence of the composition catalyst of monovalence rhodium metal catalyst and chiral diene ligand,
Amine-boron complex or azepine Cabbeen-borine 2 are entered by catalysis compound α-diazo ester shown in formulas below or ketone 1
The asymmetric insertion reaction of row boron-hydrogen bond, thus form the chirality containing alpha-carbonyl shown in structural formula 3 or ent-3 and have
Machine boranes compound；
In formula,
Ar is unsubstituted or substituted C6-C30Aryl, wherein said replacement refer to have one or more (as
1-5) substituent group, wherein said substituent group is selected from lower group: halogen, C1-6Alkyl, C1-6Haloalkyl,
C1-6Alkoxyl, C1-6Halogenated alkoxy, benzyloxy or a combination thereof；Described halogen be F, Cl, Br or
I；
R1For C1-6Alkyl, C1-6Haloalkyl, unsubstituted or substituted C6-C30Aryl, aryl are substituted
C1-6Alkyl, C1-6Alkoxyl, C1-6The substituted C of halogenated alkoxy, aryloxy or aryl1-6Alkoxyl；
Wherein said aryl is phenyl or the phenyl that replaced by one or more substituent groups selected from lower group: halogen
Element, C1-6Alkyl, C1-6Haloalkyl, nitro；Described halogen is F, Cl, Br, I；
X is C1-24Three grades of alkyl tertiary amines or azepine Cabbeen.
2. the method for claim 1, it is characterised in that wherein rhodium metal catalyst consumption be 0.5～
30mol%；And/or chiral diene ligand consumption is 0.8～30mol%；Wherein, by compound α-diazo ester
Or ketone 1 use gauge.
3. the method for claim 1, it is characterised in that described chiral diene ligand has as follows
Structural formula:
Wherein, R2And R3It is each independently substituted or unsubstituted phenyl, naphthyl or other aryl, institute
The substituent group stated is selected from lower group: halogen, unsubstituted or C by one or more halogen substiuted1-6Alkyl or
Unsubstituted or C by one or more halogen substiuted1-6Alkoxyl.
4. the method for claim 1, it is characterised in that described chiral diene ligand is selected from lower group:
5. the method for claim 1, it is characterised in that described monovalence rhodium metal is selected from lower group:
[Rh(C2H4)2Cl]2、[Rh(C2H4)2OH]2、[Rh(coe)2Cl]2、[Rh(coe)2OH]]2、[Rh(C2H4)2OMe]2、
[Rh(coe)2OMe]2Or a combination thereof.
6. the method for claim 1, it is characterised in that described borane reactant 2 is selected from lower group
Borine reaction substrate: C1-24Three grades of alkyl tertiary amine-boron complexs or azepine Cabbeen-borine.
7. the method for claim 1, it is characterised in that described method has a feature selected from lower group:
(1) organic solvent described in be C1～4 halogenated alkane (preferably dichloromethane, 1.2-dichloroethanes,
Chloroform or a combination thereof)；
(2) reaction temperature is at 15-50 DEG C；
(3) response time is 0.1-48 hour.
8. the compound shown in a structural formula 3 or ent-3, it is characterised in that
In formula,
Ar、X、R1As defined in claim 1,
Z is O or OR5, wherein R5For H, C1-6Alkyl, C1-6Haloalkyl；
And it is when Z is O, describedFor double bond；When Z is OR5Time, describedFor list
Key.
9. compound as claimed in claim 8, it is characterised in that described compound is selected from lower group:
10. a chiral diene ligand, it is characterised in that described chiral diene ligand has following structure
Formula:
Wherein, R2And R3It is each independently substituted or unsubstituted phenyl, naphthyl or other aryl, institute
The substituent group stated is selected from lower group: halogen, unsubstituted or C by one or more halogen substiuted1-6Alkyl or
Unsubstituted or C by one or more halogen substiuted1-6Alkoxyl；
And R2And R3It is different.
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| CN108341757A (en) * | 2017-01-25 | 2018-07-31 | 中国科学院上海药物研究所 | Chiral amino acid esters compound and preparation method and purposes |
| CN109053475A (en) * | 2018-07-13 | 2018-12-21 | 南京工业大学 | A kind of application of surface modified sewage sludge Pd/carbon catalyst in Cabbeen insertion N-H reaction |
| CN110669063A (en) * | 2018-07-02 | 2020-01-10 | 南开大学 | Alpha-boryl ketone and preparation method and application thereof |
| CN110669062A (en) * | 2018-07-02 | 2020-01-10 | 南开大学 | Alpha-aryl or alkyl substituted borane adducts and methods of preparation and use thereof |
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- 2015-02-15 CN CN201510083081.0A patent/CN105985365B/en active Active
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108341757A (en) * | 2017-01-25 | 2018-07-31 | 中国科学院上海药物研究所 | Chiral amino acid esters compound and preparation method and purposes |
| CN110669063A (en) * | 2018-07-02 | 2020-01-10 | 南开大学 | Alpha-boryl ketone and preparation method and application thereof |
| CN110669062A (en) * | 2018-07-02 | 2020-01-10 | 南开大学 | Alpha-aryl or alkyl substituted borane adducts and methods of preparation and use thereof |
| CN109053475A (en) * | 2018-07-13 | 2018-12-21 | 南京工业大学 | A kind of application of surface modified sewage sludge Pd/carbon catalyst in Cabbeen insertion N-H reaction |
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