CN104610355B - Indole framework based center chirality sulfonamides monophosphine ligand and preparation method - Google Patents
Indole framework based center chirality sulfonamides monophosphine ligand and preparation method Download PDFInfo
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- 0 CC(C)(C)[S@@](N=Cc1c(*)[n](C)c2ccccc12)=O Chemical compound CC(C)(C)[S@@](N=Cc1c(*)[n](C)c2ccccc12)=O 0.000 description 1
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Abstract
The invention discloses an indole framework based center chirality sulfonamides monophosphine ligand and a preparation method thereof. The monophosphine ligand adopts the structure of a formula I, and is prepared through adopting 2-halogenated indole formaldehyde (ketone) to obtain 2-disubstituted phosphine indole formaldehyde (ketone), and taking the 2-disubstituted phosphine indole formaldehyde (ketone) and chirality sulfonamide as raw materials to react with a nucleophilic reagent or a reducing reagent to prepare the compound of the formula I; optical pure compounds of four configurations of (R,R), (R,S), (S,S) and (S,R) can be obtained conveniently through adopting different chirality sulfonamides and different nucleophilic reagents. The monophosphine ligand is simple in framework, convenient to synthesize, easy to transform, can be applied to various metal catalyzed asymmetric reactions as well as the tertiary phosphine catalyzed reaction, and has good application prospect.(The formula I is shown in the description).
Description
Technical field
The present invention relates to part of a kind of chemical technology field and preparation method thereof, relate in particular to a kind of based on indole skeleton
Central chirality sulfinylamines monophosphorus ligand preparation method.
Background technology
In asymmetric synthesis, the catalyst system and catalyzing of chiral ligand and metal-complexing is that the synthesis target of enantioselectivity efficient, high is produced
The key of thing, wherein part is again the source of chiral induction and regulation and control.How to design and synthesize high selectivity, high catalytic activity
Chiral ligand is one of the focus of scholar's research of organising now.Chirality is a very important chiral ligand of class containing phosphine compound,
It applies quite varied in transition metal-catalyzed asymmetric reaction.At present, the phosphine compound of existing multiple chirality is applied to
The fields such as the production of chiral chemistry product and research and development.As far back as the sixties in last century, scientists has begun to chiral containing phosphine chemical combination
The research of thing, has synthesized the phosphine compound of numerous chirality.Meanwhile, the compound containing chirality, its each solid
Configurational isomer typically exhibits different catalytically active, biological activity and medical function.Therefore, in organic synthesis, medical treatment, life
In thing and pharmacy, the acquisition of a kind of latent chipal compounds whole spatial configuration isomer just seems particularly significant.At present, full configuration
The synthesis of compound or a difficult problem, its obtain main by chiral separation and with the part asymmetric synthesis of opposite configuration etc. just
Method realizes.The synthesis of the enantiomer of a lot of parts or a difficult problem.
The Phosphine ligands of most of chiralitys because chiral skeleton is complex, exist for expensive starting materials, synthetic route length, productivity low,
Transformation difficulty waits a difficult problem in various degree.Therefore, find that a kind of raw material is cheap, environmental friendliness, be prone to transformation, be easy to efficiently synthesize
The system of full configuration part has extraordinary application prospect.Traditionally, the synthesis of most Phosphine ligands is all the dinaphthalene from axial chirality
Set out with biphenyl compound, through 5 to 7 steps, can relatively low productivity reach to synthesize single chiral configuration containing phosphine compound (J.
Org.Chem.1993,58,1945；Tetrahedron.1994,50,4293；Acc.Chem.Res.2000,33,354).This
There is bigger difficulty in method, need to set up on the raw material basis of different chiral configurations when synthesizing whole configurational isomer,
The single product building this raw material configuration, and owing to synthetic route is longer, raw material is more expensive and uses chloromethyl methyl ether etc. in reaction
Toxic reagent, so that reaction condition is the harshest, and can produce environmentally harmful by-product and poisonous chemical combination in course of reaction
The problems such as the residual of thing.Development is set out with raw material business-like, cheap, by brief synthesis step, convenient, efficiently
Synthesize whole spatial configuration compounds method be problem demanding prompt solution.
Summary of the invention
A kind of based on indole skeleton the central chirality sulfenamide provided for the deficiencies in the prior art is provided
Class monophosphorus ligand and full configuration preparation method thereof, use the different metal reagents just can selectivity efficient, high, low cost, green
The chirality preparing whole spatial configuration sulfinylamines based on the indole skeleton monophosphorus ligand of environmental protection.
The object of the present invention is achieved like this:
A kind of central chirality sulfinylamines monophosphorus ligand based on indole skeleton, its structure is as follows:
R=substituted aryl, aryl, alkyl；Preferred aryl groups
R1=hydrogen, substituted aryl, aryl, alkyl, alkoxyl, aryloxy, unsaturated group, alkyl silyl；Preferably hydrogen
R2=hydrogen, substituted aryl, aryl, alkyl, unsaturated group, alkyl silyl；Preferably hydrogen, substituted aryl, aryl, alkyl
R3=hydrogen, substituted aryl, aryl, alkyl, unsaturated group, alkyl silyl；Preferably hydrogen, substituted aryl, aryl, alkyl
R4=substituted aryl, aryl, alkyl；Preferably alkyl
R5=hydrogen, substituted aryl, aryl, alkyl, alkoxyl, aryloxy, unsaturated group, alkyl silyl；Preferably alkyl
Above-claimed cpd has stable chirality, after silica column purification, obtains (R, R), (R, S), (S, S)
Or the optical pure compound of (S, R) four kinds of configurations, the general structure of its four kinds of configurations is as follows:
The central chirality sulfinylamines monophosphorus ligand based on indole skeleton that the present invention is above-mentioned, its preparation method:
The first step: 2-halogen indolecarboxaldehyde (ketone) i.e. compound 2 and various disubstituted phosphines i.e. material 3 is at metallic catalyst
The lower reaction of effect, generates 2-disubstituted phosphino-indolecarboxaldehyde (ketone) i.e. compound 4；Wherein, compound 2, material 3 with
The mol ratio of metallic catalyst is 10--20:10-20:1；Reaction temperature is-30-100 DEG C；Response time is 0.5-48h；Institute
It is dichloromethane, ethyl acetate, oxolane, ether, glycol dimethyl ether, dioxane, toluene, benzene with organic solvent
With the one in chloroform or its mixing；Described metallic catalyst is tetra-triphenylphosphine palladium or dichloro two triphenylphosphine palladium etc.；Synthesis road
Line is as follows:
Second step: 2-disubstituted phosphino-indolecarboxaldehyde (ketone) i.e. compound 4 and chiral sulfenamide i.e. compound 5 (R) or
Compound 5 (S) reacts under condensing agent effect, generates chiral sulfinimide i.e. compound 6 (R) or compound 6 (S)；
Wherein, compound 4, compound 5 (R) or compound 5 (S) are 1:1-10:1--15 with the mol ratio of condensing agent；Reaction temperature
Degree is for-30-100 DEG C；Response time is 0.5-48h；Organic solvent used be dichloromethane, ethyl acetate, oxolane,
One in ether, glycol dimethyl ether, dioxane, toluene, benzene and chloroform or its mixing；Described condensing agent be DCC,
DIC, EDCI, calcium oxide, phosphorus pentoxide, silicon dioxide, molecular sieve, anhydrous cupric sulfate, titanate esters, esters of silicon acis, anhydrous
Magnesium sulfate or anhydrous sodium sulfate；Synthetic route is as follows:
3rd step: compound 6 (R) or 6 (S) react under metallic catalyst effect from different nucleopilic reagents, obtains four kinds and stands
The 2-i.e. compound 1 (R, R) of disubstituted phosphino-chiral sulfenamide class Phosphine ligands of body configuration, 1 (R, S), 1 (S,
S) or 1 (S, R), wherein, the mol ratio of compound 6 (R) or 6 (S) and nucleopilic reagent is 1:1-10；Reaction temperature
For-100-50 DEG C；Response time is 0.1-48h；Organic solvent used is dichloromethane, ethyl acetate, oxolane, second
One in ether, glycol dimethyl ether, dioxane, toluene, benzene and chloroform or its mixing；Described nucleopilic reagent is organo-aluminium
Reagent, organotin reagent, copper lithium reagent, organosilicon reagent, organoboron reagent, grignard reagent, organolithium reagent or organic zinc
Reagent；Synthetic route is as follows:
Instant invention overcomes in prior art when synthesis is containing phosphine compound, raw material is more expensive, synthetic route length, productivity are low, anti-
The defect such as longer between Ying Shi, it is provided that a kind of raw material is cheap, be prone to transformation, be easy to efficiently synthesize the synthetic system of full configuration part.
Such part can be applicable in the asymmetric reaction of various metal catalytic, has the highest reactivity and stereo selectivity, and
Can be used for the reaction of tertiary phosphine catalysis, there is good application prospect.
Detailed description of the invention
Elaborating the present invention with specific embodiment below, the present embodiment is to enter under premised on the technology explanation of the present invention
Row is implemented, and following example contribute to understanding the present invention, but the present invention is not limited to the content of following example.
Embodiment 1 (R)-N-((R)-(3-(2-(diphenylphosphino))-N-methyl-indolyl) (phenyl) methyl)-1-hydrogen-t-butyl sulfonamide
The synthesis of [1a (R, R)]
Wherein, N2For nitrogen.
The first step: at the three-necked bottle of a 500mL, adds N-methyl-2-bromo-3-indolecarboxaldehyde (50mmol) and diphenylphosphine
(50mmol), under the atmosphere of nitrogen, add 150mL toluene, add tetra-triphenylphosphine palladium (2.5mmol), at 50 DEG C
Stirring 12h, productivity is 50%.
Second step: at the three-necked bottle of a 500mL, add N-methyl-2-diphenylphosphine-3-indolecarboxaldehyde (50mmol) and
(R)-(+)-t-butyl sulfonamide (50mmol), under the atmosphere of nitrogen, add 150mL oxolane, add tetraethyl titanate (100
Mmol), stirring 10h at 50 DEG C, productivity is 70%.1H NMR(400MHz,CDCl3, ppm): δ=9.05 (d, J
=3.6Hz, 1H), 8.50 (d, J=8.0Hz, 1H), 7.47 7.25 (m, 13H), 3.53 (s, 3H), 1.24 (s, 8H).13C NMR
(100MHz,CDCl3, ppm): δ=158.16,157.99,141.56,141.24,140.15,133.78,133.69,133.41,
133.33,132.37,132.19,132.14,131.96,129.08,129.04,129.02,128.97,128.86,126.00,125.96,
124.74,123.01,122.71,122.58,109.95,57.05,32.73,32.64,22.61.31P NMR(162MHz,CDCl3,
Ppm): δ=-32.64.
3rd step: the imines (1.91g, 5mmol) prepared by second step adds in the eggplant shaped reaction bottle of 50mL, and nitrogen is protected
Protect, add 15mL oxolane.At-50 DEG C, adding phenyl lithium (10mmol), be stirred overnight, productivity is 70%.1H NMR(400MHz,CDCl3, ppm): δ=7.81 (dt, J=8.2,1.0Hz, 1H), 7.53 (dd, J=7.4,1.7Hz, 2H),
7.45 (td, J=7.8,1.6Hz, 2H), 7.37 7.04 (m, 14H), 6.70 (dd, J=6.9,4.5Hz, 1H), 4.20 (d, J=4.5
Hz,1H),3.19(s,3H),1.28(s,9H).13C NMR(100MHz,CDCl3, ppm): δ=142.74,140.29,134.92,
134.82,134.54,134.45,131.80,131.63,130.18,129.88,129.74,129.44,128.78,128.75,128.72,
128.69,128.22,128.19,127.52,127.50,126.84,125.28,125.20,123.69,120.79,119.83,109.91,
56.95,56.75,56.16,32.56,32.54,22.89.31P NMR(162MHz,CDCl3, ppm): δ=-34.80.HRMS
(ESI):calculated for C32H33N2OPS[M+Na]+:547.1943,found:547.1943.[α]D 20=-49.2 (c=0.50,
CHCl3)。
Embodiment 2 (R)-N-((S)-(3-(2-(diphenylphosphino))-N-methyl-indolyl) (phenyl) methyl)-1-hydrogen-t-butyl sulfonamide
The synthesis of [1a (R, S)]
Other operate reference example 1, and nucleopilic reagent used is phenyl-magnesium-bromide, and productivity is 63%.1H NMR(400MHz,CDCl3,
Ppm): δ=7.79 (d, J=8.1Hz, 1H), 7.51 (t, J=8.4Hz, 4H), 7.42 6.99 (m, 14H), 6.73 (dd, J=8.2,
3.8Hz, 1H), 4.17 (d, J=3.8Hz, 1H), 3.22 (s, 3H), 1.19 (s, 9H).13C NMR(100MHz,CDCl3,ppm):
δ=142.92,140.26,135.10,135.00,134.30,134.22,131.87,131.77,131.70,131.59,130.92,130.62,
128.68,128.64,128.63,128.58,128.35,128.14,128.11,127.97,127.68,126.96,126.88,125.51,
125.44,123.46,121.59,119.39,109.64,56.50,56.28,55.52,32.46,22.83.31P NMR(162MHz,
CDCl3, ppm): δ=-34.99.IR (neat): 2920,1456,1056,911,741,696；HRMS(ESI):calculated for
C32H33N2OPS[M+Na]+:547.1943,found:547.1947.[α]D 20=-125.9 (c=0.50, CHCl3)。
Embodiment 3 (R)-N-((S)-(3-(2-(diphenylphosphino))-N-methyl-indolyl) (methyl) methyl)-1-hydrogen-t-butyl sulfonamide
The synthesis of [1b (R, S)]
Other operate reference example 1, and nucleopilic reagent is methyl bromide azoviolet, and gross production rate is 70%.1H NMR(400MHz,
CDCl3, ppm): δ=7.87 (d, J=8.1Hz, 1H), 7.46 (d, J=7.6Hz, 2H), 7.40 7.21 (m, 8H), 7.12 (d, J
=8.0Hz, 1H), 5.49 (d, J=4.3Hz, 1H), 3.92 3.71 (m, 1H), 3.24 (d, J=1.5Hz, 3H), 1.71 (d, J=
6.7Hz,3H),1.11(s,9H).13C NMR(100MHz,CDCl3, ppm): δ=140.16,135.28,135.18,134.63,
134.54,131.81,131.64,131.46,129.77,129.59,129.49,129.30,128.70,128.64,128.58,128.14,
128.10,125.19,125.11,123.38,121.07,119.16,109.72,55.18,49.30,49.10,32.33,32.30,24.96,
22.65.31P NMR(162MHz,CDCl3, ppm): δ=-34.98.IR (neat): 2959,1433,1362,1052,908,740,
695；HRMS(ESI):calculated for C27H31N2OPS[M+Na]+:485.1787,found:485.1774.[α]D 20=
-117.6 (c=0.50, CHCl3)。
Embodiment 4 (R)-N-((S)-(3-(2-(diphenylphosphino))-N-methyl-indolyl) (cyclohexyl base) methyl)-1-hydrogen-tert-butyl group Asia sulphur
The synthesis of amide [1c (R, S)]
Other operate reference example 1, raw materials used be (R)-(+)-t-butyl sulfonamide, nucleopilic reagent is cyclohexyl bromination azoviolet,
Gross production rate is 6%.1H NMR(400MHz,CDCl3, ppm): δ=7.91 7.72 (m, 1H), 7.50 (dd, J=10.6,5.3
Hz, 2H), 7.42 7.18 (m, 11H), 7.10 (t, J=7.1Hz, 1H), 5.16 (s, 1H), 4.07 3.73 (m, 1H), 3.20 (s,
3H),2.31–1.94(m,2H),1.93–1.69(m,1H),1.64–0.60(m,16H).13C NMR(100MHz,CDCl3,
: δ=135.74,134.70,134.61,131.97,131.80,131.55,128.63,128.58,128.53,128.01,123.40, ppm)
122.07,119.03,109.60,58.66,55.30,55.13,43.00,32.60,31.95,30.91,30.76,29.73,29.39,26.11,
26.08,26.05,22.78,22.73,14.17.31P NMR(162MHz,CDCl3, ppm): δ=-36.21.IR (neat): 2921,
1457,1056,910,741,696；HRMS(ESI):calculated for C27H31N2OPS[M+Na]+:553.2413,found:
553.2404.[α]D 20=-109.6 (c=0.50, CHCl3)。
Embodiment 5 (R)-N-((S)-(3-(2-(diphenylphosphino))-N-methyl-indolyl) (p-methoxyphenyl) methyl)-1-hydrogen-tert-butyl group
The synthesis of sulfenamide [1d (R, S)]
Other operate reference example 1, and nucleopilic reagent is 4-methoxyphenyl-magnesium bromide reagent, and gross production rate is 73%.1H NMR(400
MHz,CDCl3, ppm): δ=7.79 (d, J=8.1Hz, 1H), 7.50 (t, J=7.8Hz, 2H), 7.41 (d, J=8.7Hz, 2H),
7.36 7.18 (m, 11H), 7.06 (d, J=8.0, Hz, 1H), 6.75 (d, J=8.8Hz, 2H), 6.67 (dd, J=8.0,3.8Hz,
1H), 4.11 (d, J=3.8Hz, 1H), 3.72 (s, 3H), 3.23 (s, 3H), 1.18 (s, 9H).13C NMR(100MHz,CDCl3,
: δ=158.42,140.27,135.19,135.11,135.00,134.39,134.30,131.84,131.76,131.67,131.58, ppm)
130.69,130.39,128.67,128.63,128.62,128.57,128.26,128.16,128.15,128.12,128.09,127.97,
125.50,125.43,123.44,121.65,119.35,113.70,109.63,56.11,55.89,55.48,55.18,32.44,32.43,
22.81.31P NMR(162MHz,CDCl3, ppm): δ=-34.89.IR (neat): 2959,1609,1509,1243,1168,
1166,824,742,697；HRMS(ESI):calculated for C33H35N2O2PS[M+Na]+:577.2049,found:
577.2044.[α]D 20=-111.4 (c=0.50, CHCl3)。
Embodiment 6 (R)-N-((S)-(3-(2-(diphenylphosphino))-N-methyl-indolyl) (1-naphthyl) methyl)-1-hydrogen-tert-butyl group sulfenyl
The synthesis of amine [1e (R, S)]
Other operate reference example 1, and nucleopilic reagent is 1-naphthyl-magnesium bromide reagent, and productivity is 46%.1H NMR(400MHz,
CDCl3, ppm): δ=8.49 8.23 (m, 1H), 7.97 7.84 (m, 2H), 7.79 7.59 (m, 3H), 7.56 7.43 (m,
2H), 7.43 6.83 (m, 15H), 4.15 (d, J=2.3Hz, 1H), 3.32 (s, 3H), 1.15 (s, 9H).13C NMR(100MHz,
CDCl3, ppm): δ=140.26,137.10,134.99,134.90,134.10,134.02,133.89,132.26,132.25,132.07,
131.79,131.61,131.52,131.23,130.50,128.62,128.57,128.54,128.49,128.43,128.28,128.18,
127.93,126.63,126.56,126.23,125.74,125.51,125.49,125.45,124.89,124.11,124.06,123.19,
122.43,119.27,109.55,55.39,52.99,52.77,32.54,32.51,22.72.31P NMR(162MHz,CDCl3,ppm):
δ=-34.92.IR (neat): 3051,1433,1066,778,741,696；HRMS(ESI):HRMS(ESI):calculated for
C36H35N2OPS[M+Na]+:597.2100,found:597.2086.[α]D 20=-30.8 (c=0.50, CHCl3)。
Embodiment 7 (R)-N-((R)-(3-(2-(diphenylphosphino))-N-methyl-indolyl) (p-methoxyphenyl) methyl)-1-hydrogen-tert-butyl group
The synthesis of sulfenamide [1f (R, R)]
Other operate reference example 1, and nucleopilic reagent is 4-methoxyphenyl lithium reagent, and productivity is 21%.1H NMR(400MHz,
CDCl3, ppm): δ=7.84 (d, J=8.1,1H), 7.49 7.39 (m, 4H), 7.38 7.19 (m, 10H), 7.10 (d, J=8.0
Hz, 1H), 6.73 (d, J=8.7Hz, 2H), 6.63 (dd, J=6.7,4.3Hz, 1H), 4.15 (d, J=4.3Hz, 1H), 3.72 (s,
3H),3.19(s,3H),1.27(s,9H).13C NMR(100MHz,CDCl3, ppm): δ=158.44,140.27,134.93,
134.87,134.84,134.65,134.55,131.79,131.74,131.62,131.57,130.32,130.03,129.55,129.25,
128.72,128.70,128.66,128.64,128.16,128.14,125.28,125.21,123.61,120.90,119.74,113.55,
109.86,56.46,56.27,56.00,55.20,55.18,32.51,32.49,22.86.31P NMR(162MHz,CDCl3,ppm):δ
=-34.77.IR (neat): 2950,1609,1509,1460,1361,1243,1170,1070,823,742,696；HRMS(ESI):
calculated for C33H35N2O2PS[M+Na]+:577.2049,found:577.2031.[α]D 20=-50.6 (c=0.50,
CHCl3)。
Embodiment 8 (R)-N-((R)-(3-(2-(diphenylphosphino))-N-methyl-indolyl) (m-methoxyphenyl) methyl)-1-hydrogen-tert-butyl group
The synthesis of sulfenamide [1g (R, R)]
Other operate reference example 1, and nucleopilic reagent is 3-methoxyphenyl lithium reagent, and productivity is 70%.1H NMR(400MHz,
CDCl3, ppm): δ=7.83 (d, J=8.0Hz, 1H), 7.56 7.38 (m, 2H), 7.37 7.18 (m, 11H), 7.18 7.01
(m, 4H), 6.78 6.62 (m, 2H), 4.16 (d, J=4.3Hz, 1H), 3.52 (s, 3H), 3.18 (s, 3H), 1.29 (s, 9H).13C
NMR(100MHz,CDCl3, ppm): δ=159.37,144.35,140.21,134.98,134.88,134.35,134.26,131.80,
131.62,131.44,130.14,129.83,129.51,129.20,129.07,128.72,128.67,128.61,128.17,128.11,
125.04,124.97,123.62,120.68,119.76,119.58,119.56,112.79,112.56,112.54,109.82,56.79,
56.59,56.07,54.81,32.46,22.82.31P NMR(162MHz,CDCl3, ppm): δ=-34.97.IR (neat): 1596,
1455,1264,1068,863,742,697；HRMS(ESI):calculated for C33H35N2OPS[M+Na]+:577.2049,
found:577.2062.[α]D 20=-55.1 (c=0.50, CHCl3)。
Embodiment 9 (R)-N-((S)-(3-(2-(diphenylphosphino))-N-methyl-indolyl) (3,5-di-t-butyl-4-methoxyphenyl) first
Base) synthesis of-1-hydrogen-t-butyl sulfonamide [1h (R, S)]
Other operate reference example 1, and nucleopilic reagent is 3,5-dimethoxy-4 '-methoxyphenyl-magnesium bromide reagent, and productivity is 72%.1H NMR(400MHz,CDCl3, ppm): δ=8.00 7.89 (m, 1H), 7.54 (t, J=7.2Hz, 2H), 7.42 (s, 2H),
7.37 7.15 (m, 8H), 7.08 (ddd, J=8.1,5.2,2.8Hz, 1H), 6.72 (dd, J=8.9,2.8Hz, 1H), 4.06 (d, J=
2.9Hz,1H),3.58(s,3H),3.20(s,3H),1.68–1.54(m,2H),1.25(s,9H),1.24(s,16H).13C NMR
(100MHz,CDCl3, ppm): δ=158.12,143.25,140.28,136.77,135.73,135.62,134.03,133.94,
132.09,131.92,131.54,131.36,131.03,130.73,128.72,128.66,128.59,128.11,128.05,127.96,
127.81,125.42,125.34,125.17,123.28,122.06,119.10,109.64,63.95,56.39,56.15,55.33,35.61,
32.43,31.94,31.84,23.02.31P NMR(162MHz,CDCl3, ppm): δ=-34.95.IR (neat): 2954,1608,
1502,1242,1169,1165,823,741,697；HRMS(ESI):HRMS(ESI):calculated for
C41H51N2O2PS[M+Na]+:689.3301,found:689.3290.[α]D 20=-126.2 (c=0.50, CHCl3)。
Embodiment 10 (R)-N-((S)-(3-(2-(diphenylphosphino))-N-methyl-indolyl) (2-naphthyl) methyl)-1-hydrogen-tertiary fourth
The synthesis of base sulfenamide [1i (R, S)]
Other operate reference example 1, and nucleopilic reagent is 2-naphthyl-magnesium bromide reagent, and productivity is 53%.1H NMR(400MHz,
CDCl3, ppm): δ=7.98 (d, J=1.5Hz, 1H), 7.81 (dt, J=8.1,1.0Hz, 1H), 7.74 7.61 (m, 3H), 7.52
(tt, J=7.7,1.8Hz, 3H), 7.43 7.15 (m, 11H), 7.03 (ddd, J=8.0,5.0,3.0Hz, 1H), 6.87 (dd, J=8.2,
4.0Hz,1H),3.25(s,3H),1.22(s,9H).13C NMR(100MHz,CDCl3, ppm): δ=140.48,140.39,
135.18,135.08,134.42,134.33,133.27,132.52,132.05,131.88,131.69,131.03,130.73,128.81,
128.75,128.73,128.67,128.26,128.23,128.15,128.10,127.90,127.60,127.50,125.98,125.74,
125.68,125.63,125.62,125.60,125.33,125.32,123.58,121.57,119.55,109.72,56.77,56.55,
55.69,32.56,32.55,22.93.IR(neat):2948,1460,1360,1064,874,741,696；31P NMR(162MHz,
CDCl3, ppm): δ=-34.88.HRMS (ESI): calculated for C36H35N2OPS[M+Na]+:597.2100,found:
597.2077.[α]D 20=-157.9 (c=0.50, CHCl3)。
Embodiment 11 (R)-N-((S)-(3-(2-(diphenylphosphino))-N-methyl-indolyl) (phenyl) methyl)-1-hydrogen-tert-butyl group Asia sulphur
The synthesis of amide [1j (R, S)]
Other operate reference example 1, nucleopilic reagent be between phenyl phenyl-magnesium-bromide reagent, productivity is 71%.1H NMR(400MHz,
CDCl3, ppm): δ=7.87 (dt, J=8.2,1.0Hz, 1H), 7.71 7.58 (m, 2H), 7.54 (td, J=7.9,1.5Hz, 2H),
7.42 7.17 (m, 17H), 7.07 (ddd, J=8.0,4.9,3.1Hz, 1H), 6.84 (dd, J=8.7,3.5Hz, 1H), 4.21 (d, J
=3.6Hz, 1H), 3.23 (s, 3H), 1.24 (s, 9H).13C NMR(100MHz,CDCl3, ppm): δ=143.53,141.11,
140.74,140.33,135.27,132.10,131.93,131.65,131.47,128.80,128.74,128.69,128.63,128.58,
128.20,128.10,127.03,126.94,126.18,126.16,125.62,125.21,123.52,121.60,119.46,109.70,
56.53,56.30,55.55,32.48,22.92.31P NMR(162MHz,CDCl3, ppm): δ=-35.26.IR (neat): 2951,
1457,1063,741,696；HRMS(ESI):calculated for C38H37N2OPS[M+Na]+:623.2256,found:
623.2236.[α]D 20=-96.4 (c=0.50, CHCl3)。
Embodiment 12 (R)-N-((S)-(3-(2-(diphenylphosphino))-N-methyl-indolyl) (adjacent phenyl) methyl)-1-hydrogen-tert-butyl group Asia sulphur
The synthesis of amide [1k (R, S)]
Other operate reference example 1, and nucleopilic reagent is adjacent phenyl magnesium bromide reagent, and productivity is 48%.1H NMR(400MHz,
CDCl3, ppm): δ=7.66 (d, J=8.2Hz, 1H), 7.61 7.06 (m, 9H), 7.02 (dt, J=7.7,3.6Hz, 1H), 3.20
(s,3H),0.94(s,9H).13C NMR(100MHz,CDCl3, ppm): δ=141.16,140.58,140.30,139.67,
135.32,135.21,134.71,134.62,131.91,131.78,131.73,131.61,131.00,129.33,129.32,128.90,
128.71,128.66,128.63,128.57,128.14,127.97,127.75,127.50,127.44,126.88,126.80,126.68,
126.39,123.45,122.84,119.37,109.63,55.16,53.44,53.21,32.64,22.78,22.62.31P NMR(162
MHz,CDCl3, ppm): δ=-24.57.IR (neat): 1433,1068,742,694；HRMS(ESI):calculated for
C38H37N2OPS[M+Na]+:623.2256,found:623.2250.[α]D 20=18.4 (c=0.50, CHCl3)。
Embodiment 13 (R)-N-((S)-(3-(2-(diphenylphosphino))-N-methyl-indolyl) (cyclopropyl) methyl)-1-hydrogen-t-butyl sulfonamide
The synthesis of [1l (R, S)]
Other operate reference example 1, and nucleopilic reagent is cyclopropyl bromination azoviolet, and productivity is 44%.1H NMR(400MHz,
CDCl3, ppm): δ=7.95 (d, J=8.0Hz, 1H), 7.49 (td, J=7.8,1.5Hz, 2H), 7.42 7.21 (m, 10H),
7.12 (ddd, J=8.0,6.0,1.9Hz, 1H), 4.56 (ddd, J=9.8,7.2,2.5Hz, 1H), 3.88 (s, 1H), 3.20 (s, 3H),
1.15 (s, 9H), 0.78 0.61 (m, 1H), 0.54 (dd, J=9.7,4.9Hz, 1H), 0.32m, 1H) and, 0.21 (d, J=9.7,1H).13C NMR(100MHz,CDCl3, ppm): δ=140.35,135.53,135.43,135.06,134.97,131.77,131.75,
131.60,131.57,128.64,128.59,128.58,128.07,128.02,123.46,121.58,119.16,109.6858.73,
58.52,55.09,32.46,22.79,18.95,5.74,4.36,4.34.31P NMR(162MHz,CDCl3, ppm): δ=-35.48.
IR(neat):2948,1458,1361,1060,816,741,696；HRMS(ESI):calculated for
C29H33N2OPS[M+Na]+:511.1943,found:511.1924.[α]D 20=-115.1 (c=0.50, CHCl3)。
Embodiment 14 (R)-N-((R)-(3-(2-(diphenylphosphino))-N-methyl-indolyl) (normal-butyl) methyl)-1-hydrogen-tert-butyl group sulfenyl
The synthesis of amine [1m (R, R)]
Other operate reference example 1, and nucleopilic reagent is reagent n-butyllithium, and productivity is 23%.1H NMR(400MHz,CDCl3,
Ppm): δ=7.86 (d, J=8.0Hz, 1H), 7.51 7.21 (m, 12H), 7.14 (ddd, J=8.0,6.3,1.5Hz, 1H), 5.32
(dq, J=10.0,5.5Hz, 1H), 3.88 (d, J=4.0Hz, 1H), 3.19 (s, 3H), 2.12 (dt, J=8.5,4.9Hz, 1H), 1.22
(s,9H),1.18–0.95(m,1H),0.64(m,3H).13C NMR(100MHz,CDCl3, ppm): δ=140.19,135.48,
135.38,134.75,134.66,131.91,131.74,131.56,131.39,129.91,129.73,129.61,129.43,128.72,
128.71,128.67,128.65,128.20,128.09,125.51,125.43,123.57,120.67,119.45,109.84,55.67,
53.73,53.55,36.63,32.56,32.54,29.02,22.74,22.52,13.87.31P NMR(162MHz,CDCl3,ppm):δ
=-35.37.IR (neat): 2948,1458,1060,741,696；HRMS(ESI):calculated for
C32H33N2OPS[M+Na]+:527.2256,found:527.2271.[α]D 20=-37.2 (c=0.50, CHCl3)。
Embodiment 15 (R)-N-((R)-(3-(2-(diphenylphosphino))-N-methyl-indolyl) (3,5-Dimethoxyphenyl) methyl)-1-hydrogen-tertiary fourth
The synthesis of base sulfenamide [1n (R, R)]
Other operate reference example 1, and nucleopilic reagent is 3,5-Dimethoxyphenyl lithium reagent, and productivity is 26%.1H NMR(400MHz,
CDCl3, ppm): δ=7.91 7.84 (d, J=8.1,1H), 7.52 7.41 (m, 2H), 7.38 7.21 (m, 8H), 4.15 (t, J=
3.2Hz, 1H), 3.49 (d, J=1.4Hz, 6H), 3.17 (s, 3H), 1.32 (s, 9H).13C NMR(100MHz,CDCl3,ppm):
δ=159.37,144.35,140.21,134.98,134.88,134.35,134.26,131.80,131.62,131.44,130.14,129.83,
129.51,129.20,129.07,128.72,128.67,128.61,128.17,128.11,125.04,124.97,123.62,120.68,
119.76,119.58,119.56,112.79,112.56,112.54,109.82,56.79,56.59,56.07,54.90,54.81,32.46,
22.82.IR(neat):1595,1458,1324,1203,1153,1055,826,743,695；31P NMR(162MHz,CDCl3,
Ppm): δ=-35.08.HRMS (ESI): calculated for C27H31N2OPS[M+Na]+:607.2155,found:607.2165.
[α]D 20=-115.2 (c=0.50, CHCl3)。
Embodiment 16 (R)-N-((R)-(3-(2-(diphenylphosphino))-N-methyl-indolyl) (2-naphthyl) methyl)-1-hydrogen-tert-butyl group
The synthesis of sulfenamide [1o (R, R)]
Other operate reference example 1, and nucleopilic reagent is 2-naphthyl lithium reagent, and productivity is 63%.1H NMR(400MHz,CDCl3,
Ppm): δ=7.98 (d, J=1.5Hz, 1H), 7.87 (d, J=7.9Hz, 1H), 7.75 7.56 (m, 5H), 7.46 (dt, J=7.4,
3.4Hz, 3H), 7.42 7.16 (m, 14H), 7.08 (d, J=7.9Hz, 1H), 6.86 (dd, J=6.8,4.1Hz, 1H), 4.32 (d,
J=4.9Hz, 1H), 3.20 (s, 3H), 1.32 (s, 9H).13C NMR(100MHz,CDCl3, ppm): δ=140.24,140.16,
134.90,134.80,134.41,134.32,133.14,132.45,131.84,131.80,131.66,131.62,129.84,129.79,
129.54,129.48,128.78,128.76,128.73,128.70,128.23,128.05,127.94,127.47,126.22,126.20,
125.84,125.81,125.65,125.29,125.21,123.68,120.75,119.87,109.91,57.11,56.92,56.18,32.58,
22.91.31P NMR(162MHz,CDCl3, ppm): δ=-34.57.IR (neat): 2949,1461,1362,1066,872,741,
696；HRMS(ESI):calculated for C36H35N2OPS[M+Na]+:597.2100,found:597.2105.[α]D 20=-40.1
(c=0.50, CHCl3)。
Embodiment 17 (R)-N-((R)-(3-(2-(diphenylphosphino))-N-methyl-indolyl) (to ethoxyl phenenyl) methyl)-1-hydrogen-tert-butyl group
The synthesis of sulfenamide [1p (R, R)]
Other operate reference example 1, and nucleopilic reagent is 4-ethoxyl phenenyl lithium reagent, and productivity is 64%.1H NMR(400MHz,
CDCl3, ppm): δ=7.83 (d, J=8.0Hz, 1H), 7.49 7.36 (m, 4H), 7.36 7.16 (m, 10H), 7.09 (d, J=
7.9,1H), 4.14 (dd, J=4.4,1.5Hz, 1H), 3.93 (q, J=6.9Hz, 2H), 3.17 (s, 3H), 1.34 (dd, J=7.4,6.5
Hz,3H),1.26(s,9H).13C NMR(100MHz,CDCl3, ppm): δ=157.83,140.28,134.95,134.86,
134.72,134.68,134.59,131.81,131.76,131.63,131.58,130.37,130.08,129.56,129.25,128.72,
128.71,128.67,128.65,128.16,128.14,125.33,125.25,123.61,120.94,119.74,114.14,109.86,
63.34,56.50,56.31,56.00,32.52,32.50,22.87,14.85.31P NMR(162MHz,CDCl3, ppm): δ=
-34.86.IR(neat):2956,1608,1508,1240,1169,1074,822,742,696；HRMS(ESI):calculated for
C34H37N2O2PS[M+Na]+:591.2206,found:591.2208.[α]D 20=-64.0 (c=0.50, CHCl3)。
Embodiment 18 (R)-N-((R)-(3-(2-(diphenylphosphino))-N-methyl-indolyl) (1-naphthyl) methyl)-1-hydrogen-t-butyl sulfonamide
The synthesis of [1q (R, R)]
Other operate reference example 1, and nucleopilic reagent is 1-naphthyl lithium reagent, and productivity is 23%.1H NMR(400MHz,CDCl3,
Ppm): δ=8.24 (d, J=8.0Hz, 1H), 8.12 (d, J=7.3Hz, 1H), 7.77 7.68 (m, 2H), 7.64 (d, J=8.2Hz,
1H), 7.54 (td, J=7.9,1.5Hz, 2H), 7.50 7.12 (m, 11H), 6.94 (d, J=15.4Hz, 2H), 4.22 (d, J=4.6
Hz,1H),3.23(s,3H),1.25(s,9H).13C NMR(100MHz,CDCl3, ppm): δ=140.28,137.40,134.89,
134.79,134.55,134.46,133.97,132.10,131.93,131.91,131.18,130.13,129.83,129.00,128.82,
128.78,128.72,128.70,128.50,128.30,128.27,128.10,125.92,125.85,125.60,125.51,125.49,
125.34,124.82,124.77,124.75,123.48,120.86,120.84,119.72,109.72,56.29,54.34,54.14,32.74,
22.85.31P NMR(162MHz,CDCl3, ppm): δ=-35.14.IR (neat): 2955,1362,1070,814,742,696；
HRMS(ESI):calculated for C36H35N2OPS[M+Na]+:597.2100,found:597.2115.[α]D 20=-52.6 (c=
0.50,CHCl3)。
Embodiment 19 (R)-N-((R)-(3-(2-(diphenylphosphino))-N-methyl-indolyl) (p-trifluoromethyl phenyl) methyl)-1-hydrogen-tertiary fourth
The synthesis of base sulfenamide [1r (R, R)]
Other operate reference example 1, and nucleopilic reagent is 4-trifluoromethyl lithium reagent, and productivity is 19%.1H NMR(400MHz,
CDCl3, ppm): δ=7.83 (d, J=8.0Hz, 1H), 7.62 (d, J=8.0Hz, 2H), 7.48 7.36 (m, 3H), 7.34 7.19
(m, 7H), 7.12 (t, J=1.4Hz, 1H), 6.83 6.66 (m, 1H), 4.24 (d, J=4.3Hz, 1H), 3.21 (s, 3H), 1.29
((s,9H).13C NMR(100MHz,CDCl3, ppm): δ=146.99,140.27,134.71,134.61,133.91,133.83,
131.89,131.78,131.72,131.60,131.11,130.81,129.24,128.92,128.88,128.83,128.78,128.72,
128.40,128.37,127.32,127.31,127.17,126.87,125.42,125.38,125.34,125.31,125.28,125.20,
123.75,121.03,119.76,109.92,56.43,56.21,55.78,32.58,32.56,22.84.31P NMR(162MHz,
CDCl3, ppm): δ=-34.42.IR (neat): 1323,1161,1119,1066,824,742,698；HRMS(ESI):
calculated for C33H32N2OPS[M+Na]+:615.1817,found:615.1810.[α]D 20=-44.3 (c=0.50, CHCl3)。
Embodiment 20 (R)-N-((R)-(3-(2-(diphenylphosphino))-N-methyl-indolyl) (3,5-3,5-dimethylphenyl) methyl)-1-hydrogen-tert-butyl group
The synthesis of sulfenamide [1s (R, R)]
Other operate reference example 1, and nucleopilic reagent is 3,5-3,5-dimethylphenyl lithium reagent, and productivity is 48%.1H NMR(400MHz,
CDCl3, ppm): δ=7.87 (d, J=8.1Hz, 1H), 7.44 (t, J=7.7,2H), 7.37 7.19 (m, 10H), 7.16 7.05
(m, 3H), 6.73 (s, 1H), 6.62 (d, J=6.9Hz, 1H), 4.34 4.13 (m, 1H), 3.17 (s, 3H), 2.10 (s, 6H), 1.30
(s,9H).13C NMR(100MHz,CDCl3, ppm): δ=142.59,140.21,137.50,135.12,135.02,134.54,
134.45,131.91,131.74,131.72,131.55,130.47,130.17,128.69,128.63,128.35,128.15,128.12,
125.29,125.26,125.17,123.57,120.81,119.70,109.78,56.78,56.59,56.10,32.51,22.88,21.30.31P NMR(162MHz,CDCl3, ppm): δ=-34.55.IR (neat): 2953,1458,1362,1072,849,742,696；
HRMS(ESI):calculated for C34H37N2OPS[M+Na]+:575.2256,found:575.2240.[α]D 20=-57.3 (c=
0.50,CHCl3)。
Embodiment 21 (R)-N-((R)-(3-(2-(diphenylphosphino))-N-methyl-indolyl) (3,5-di-tert-butyl-phenyl) methyl)-1-hydrogen-tertiary fourth
The synthesis of base sulfenamide [1t (R, R)]
Other operate reference example 1, and nucleopilic reagent is 3,5-di-tert-butyl-phenyl lithium reagent, and productivity is 77%.1H NMR(400MHz,
CDCl3, ppm): δ=δ 7.96 (d, J=8.0Hz, 1H), 7.53 7.19 (m, 15H), 7.13 (m, 2H), 6.80 (dt, J=7.5,
2.3Hz, 1H), 4.11 (dd, J=3.3,1.5Hz, 1H), 3.16 (s, 3H), 1.33 (s, 9H), 1.15 (d, J=1.5Hz, 18H).13C
NMR(100MHz,CDCl3, ppm): δ=150.65,150.24,141.50,140.28,135.50,135.39,134.36,134.27,
131.93,131.75,131.56,131.38,130.88,130.57,128.83,128.77,128.74,128.68,128.17,128.10,
123.57,121.69,121.67,121.13,120.73,119.59,109.87,56.01,34.73,32.56,31.39,31.31,23.09,
22.99,22.58.31P NMR(162MHz,CDCl3, ppm): δ=-35.58.IR (neat):
2950,1457,1360,1074,847,741,696；HRMS(ESI):calculated for C34H37N2OPS[M+Na]+:
659.3195,found:659.3210.[α]D 20=-49.1 (c=0.50, CHCl3)。
Claims (1)
1. a preparation method for central chirality sulfinylamines monophosphorus ligand based on indole skeleton, its ligand structure formula is as follows:
In formula:
R=aryl, alkyl；
R1=hydrogen, aryl, alkyl, alkoxyl, aryloxy, alkyl silyl；
R2=hydrogen, aryl, alkyl, alkyl silyl；
R3=hydrogen, aryl, alkyl, alkyl silyl；
R4=aryl, alkyl；
R5=hydrogen, aryl, alkyl, alkoxyl, aryloxy, alkyl silyl；
Compound 1 has stable chirality, and it has the optical pure compound of (R, R), (R, S), (S, S) or (S, R) configuration, and concrete structure formula is as follows:
It is characterized in that the method comprises the following steps:
The first step: compound 2 and material 3 react under metallic catalyst effect, generates compound 4；Wherein, compound 2, material 3 are 10-20: 10-20: 1 with the mol ratio of metallic catalyst；Reaction temperature is-30-100 DEG C；Response time is 0.5-48h；Organic solvent used is the one in dichloromethane, ethyl acetate, oxolane, ether, glycol dimethyl ether, dioxane, toluene, benzene and chloroform or its mixing；Described metallic catalyst is tetra-triphenylphosphine palladium or dichloro two triphenylphosphine palladium；Synthetic route is as follows:
Second step: compound 4 reacts under condensing agent effect with chipal compounds 5 (R) or compound 5 (S), generates chipal compounds 6 (R) or compound 6 (S)；Wherein, compound 4, compound 5 (R) or compound 5 (S) are 1: 1-10: 1-15 with the mol ratio of condensing agent；Reaction temperature is-30-100 DEG C；Response time is 0.5-48h；Organic solvent used is the one in dichloromethane, ethyl acetate, oxolane, ether, glycol dimethyl ether, dioxane, toluene, benzene and chloroform or its mixing；Described condensing agent is dicyclohexylcarbodiimide, N, N '-DIC, 1-ethyl-(3-dimethylaminopropyl) carbodiimide hydrochloride, calcium oxide, phosphorus pentoxide, silicon dioxide, molecular sieve, anhydrous cupric sulfate, titanate esters, esters of silicon acis, anhydrous magnesium sulfate or anhydrous sodium sulfate；Synthetic route is as follows:
3rd step: compound 6 (R) or 6 (S) and different organometallic reagent R3[M] reacts under metallic catalyst effect, obtain the 2-i.e. compound 1 (R of disubstituted phosphino-chiral sulfenamide class Phosphine ligands of four kinds of spatial configurations, R), 1 (R, S), 1 (S, S) or 1 (S, R), wherein, compound 6 (R) or 6 (S) and organometallic reagent R3The mol ratio of [M] is 1: 1-10；Reaction temperature is-100-50 DEG C；Response time is 0.1-48h；Organic solvent used is the one in dichloromethane, ethyl acetate, oxolane, ether, glycol dimethyl ether, dioxane, toluene, benzene and chloroform or its mixing；Described organometallic reagent R3[M] is organoaluminum reagents, organotin reagent, copper lithium reagent, organosilicon reagent, organoboron reagent, Grignard reagent, organolithium reagent or organic zinc reagent；Synthetic route is as follows:
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