CN105669766A - Spiro-framework-based cyclopentadiene compounds, rhodium complexes, and synthesis method and application thereof - Google Patents

Spiro-framework-based cyclopentadiene compounds, rhodium complexes, and synthesis method and application thereof Download PDF

Info

Publication number
CN105669766A
CN105669766A CN201610120414.7A CN201610120414A CN105669766A CN 105669766 A CN105669766 A CN 105669766A CN 201610120414 A CN201610120414 A CN 201610120414A CN 105669766 A CN105669766 A CN 105669766A
Authority
CN
China
Prior art keywords
compound
spirobindene
cyclopentadiene
alkane skeleton
organic solvent
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN201610120414.7A
Other languages
Chinese (zh)
Other versions
CN105669766B (en
Inventor
游书力
郑军
崔文俊
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Shanghai Institute of Organic Chemistry of CAS
Original Assignee
Shanghai Institute of Organic Chemistry of CAS
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Shanghai Institute of Organic Chemistry of CAS filed Critical Shanghai Institute of Organic Chemistry of CAS
Priority to CN201610120414.7A priority Critical patent/CN105669766B/en
Publication of CN105669766A publication Critical patent/CN105669766A/en
Application granted granted Critical
Publication of CN105669766B publication Critical patent/CN105669766B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
    • C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table compounds of the platinum group
    • C07F15/0073—Rhodium compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/1616—Coordination complexes, e.g. organometallic complexes, immobilised on an inorganic support, e.g. ship-in-a-bottle type catalysts
    • B01J31/1625—Coordination complexes, e.g. organometallic complexes, immobilised on an inorganic support, e.g. ship-in-a-bottle type catalysts immobilised by covalent linkages, i.e. pendant complexes with optional linking groups
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/22—Organic complexes
    • B01J31/2282—Unsaturated compounds used as ligands
    • B01J31/2295—Cyclic compounds, e.g. cyclopentadienyls
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C13/00—Cyclic hydrocarbons containing rings other than, or in addition to, six-membered aromatic rings
    • C07C13/28—Polycyclic hydrocarbons or acyclic hydrocarbon derivatives thereof
    • C07C13/32—Polycyclic hydrocarbons or acyclic hydrocarbon derivatives thereof with condensed rings
    • C07C13/72—Spiro hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C43/00—Ethers; Compounds having groups, groups or groups
    • C07C43/02—Ethers
    • C07C43/20—Ethers having an ether-oxygen atom bound to a carbon atom of a six-membered aromatic ring
    • C07C43/21—Ethers having an ether-oxygen atom bound to a carbon atom of a six-membered aromatic ring containing rings other than six-membered aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D217/00—Heterocyclic compounds containing isoquinoline or hydrogenated isoquinoline ring systems
    • C07D217/02—Heterocyclic compounds containing isoquinoline or hydrogenated isoquinoline ring systems with only hydrogen atoms or radicals containing only carbon and hydrogen atoms, directly attached to carbon atoms of the nitrogen-containing ring; Alkylene-bis-isoquinolines
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D221/00—Heterocyclic compounds containing six-membered rings having one nitrogen atom as the only ring hetero atom, not provided for by groups C07D211/00 - C07D219/00
    • C07D221/02—Heterocyclic compounds containing six-membered rings having one nitrogen atom as the only ring hetero atom, not provided for by groups C07D211/00 - C07D219/00 condensed with carbocyclic rings or ring systems
    • C07D221/04—Ortho- or peri-condensed ring systems
    • C07D221/06—Ring systems of three rings
    • C07D221/10—Aza-phenanthrenes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/40—Substitution reactions at carbon centres, e.g. C-C or C-X, i.e. carbon-hetero atom, cross-coupling, C-H activation or ring-opening reactions
    • B01J2231/42—Catalytic cross-coupling, i.e. connection of previously not connected C-atoms or C- and X-atoms without rearrangement
    • B01J2231/4205—C-C cross-coupling, e.g. metal catalyzed or Friedel-Crafts type
    • B01J2231/4261—Heck-type, i.e. RY + C=C, in which R is aryl
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
    • B01J2531/0225—Complexes comprising pentahapto-cyclopentadienyl analogues
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/80—Complexes comprising metals of Group VIII as the central metal
    • B01J2531/82—Metals of the platinum group
    • B01J2531/822—Rhodium

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

The invention relates to spiro-chiral-framework-based cyclopentadiene rhodium complexes, and a synthesis method and application thereof. The cyclopentadiene rhodium complexes have the optically pure compounds of which the structural formula is disclosed in the specification. The method provided by the invention can be used for synthesizing the rhodium complexes at high yield, and has excellent effects on axially chiral biaryl compound establishment reaction by asymmetric C-H bond oxidation Heck coupling reaction when being used as a catalyst. Particularly, the rhodium complexes usually have excellent enantioselectivity for olefin substrates. Therefore, the complexes have very important meanings for metal-rhodium-catalyzed asymmetric C-H bond functionalization reaction.

Description

Based on spirocyclic ring scaffold class cyclopentadiene compound and its rhodium complex, synthetic method and application
Technical field
The present invention relates to the cyclopentadiene compound based on spiral shell chiral skeleton and its rhodium complex, synthetic method and application, the method can synthesize this cyclopentadiene part effectively, and this part is successfully applied in the preparation of a series of metal rhodium complex. In the asymmetric oxidation Heck coupling reaction of this kind of metal rhodium complex catalysis, construct a series of axial chirality compound high enantioselectivity.
Background technology
Pentamethylcyclopentadiene rhodium complex catalyzed c h bond functionalization reaction can build carbon-carbon bond and carba key efficiently, be widely used in synthesis. But, this kind of rhodium complex catalyzed asymmetric c h bond functionalization is reacted several years up to date, has just had important breakthrough. Ward and Rovis group has successfully synthesized biotinylated [Cp*Rh (III)] complex, it is combined with Streptavidin and can be applied successfully to during asymmetric c h bond functionalization reacts. [T.K.Hyster, L.T.R.Ward, T.Rovis, Science2012,338,500 503.]. And the synthesis of this kind of catalyst is more complicated, and the suitability for great majority reaction is bad. Almost in the same time, tartaric acid derivatives skeleton is successfully attached on cyclopentadiene by Cramer group, in the cyclopentadiene part having synthesized a series of C2-symmetry the synthesis being applied to rhodium complex. This kind of rhodium complex can the hydrogen arylation reaction of catalysis benzyl hydroximic acid analog derivative of enantioselectivity efficient, high. [B.Ye, N.Cramer, Science2012,338,504 506]. Subsequently, dinaphthalene skeleton is applied in the synthesis of C2-symmetrical ring cyclopentadiene ligand again by this group, and its corresponding rhodium complex has wide using value in the reaction of asymmetric c h bond functionalization. [(a) Ye, B.; Cramer, N.J.Am.Chem.Soc.2013,135,636. (b) Ye, B.; Donets, P.A.; Cramer, N.Angew.Chem., Int.Ed.2014,53,507. (c) Ye, B.; Cramer, N.Angew.Chem., Int.Ed.2014,53,7896. (d) Zheng, J.; You, S.-L.Angew.Chem., Int.Ed.2014,53,13244. (e) Ye, B.; Cramer, N.Synlett2015,26,1490-1495. (f) Zheng, J.; Wang, S.-B.; Zheng, C.; You, S.-L.J.Am.Chem.Soc.2015,137,4880.].Not only in this, this kind of cyclopentadiene part also has been widely used in other metal. [(a) Song, G.; O, W.W.N.; Hou, Z.J.Am.Chem.Soc.2014,136,12209. (b) Dieckmann, M.; Jang, Y.-S.; Cramer, N.Angew.Chem.Int.Ed.2015,54,12149. (c) Kossler, D; Cramer, N.J.Am.Chem.Soc.2015,137,12478.]. But, the skeleton of the C2-symmetrical ring cyclopentadiene ligand of current this kind of chirality is comparatively rare, and has the enantioselectivity of some reactions to control or bad. In order to solve these problems, and the skeleton of the C2-symmetrical ring cyclopentadiene ligand of abundant this kind of chirality we design and synthesized a series of cyclopentadiene part based on spiral shell chiral skeleton, these parts can form rhodium complex with metal rhodium effect, and asymmetric c h bond is activated, and the reaction building biaryl axial chirality compound has extraordinary catalytic effect. Especially for olefines substrate, generally extraordinary enantioselectivity can be obtained. Therefore these parts and complex all have very important significance for the expansion of the c h bond functionalization reaction substrate scope of metal rhodium catalysis and the abundant of response type.
Summary of the invention
It is an object of the invention to provide a kind of optically pure cyclopentadiene compounds with spirocyclic ring scaffold and its corresponding rhodium complex, their synthetic method, and be applied to catalysis asymmetric c h bond oxidation Heck coupling reaction structure biaryl axial chirality compound.
The method of the present invention is the method for its corresponding metal rhodium complex of cyclopentadiene compou nd synthesis of a kind of effective spirocyclic ring scaffold.
Optical voidness volution framework ring pentadiene rhodium complex synthesized by the present invention can be applied in asymmetric c h bond oxidation Heck coupling reaction, can obtain biaryl axial chirality compound with high efficiency and enantioselectivity.
The structural formula of spirocyclic ring scaffold cyclopentadiene rhodium complex of the present invention is:
Or its enantiomerOptical pure compound; Wherein, R1Selected from H, C1～C16 alkyl, C1～C16 perfluoroalkyl, C1～C16 alkoxyl or benzyloxy.
Present invention also offers the cyclopentadiene compound of 1,1'-spirobindene alkane skeleton as shown in formula (S)-I, (R)-I, (S)-I ' or (R)-I ',
Wherein, R1Selected from H, C1～C16 alkyl, C1～C16 perfluoroalkyl, C1～C16 alkoxyl or benzyloxy.
The cyclopentadiene rhodium complex of spirocyclic ring scaffold of the present invention is in organic solvent to have the cyclopentadiene of 1,1'-spirobindene alkane skeleton, ethanol thallium, [Rh (C2H4)2Cl]2For raw material, reaction prepares, and available formulas below 1 and 2 represents:
Reaction equation 1:
Reaction equation 2:
In above reaction equation, solvents represents organic solvent; Wherein R1Selected from H, C1～C16 alkyl, C1～C16 perfluoroalkyl, C1～C16 alkoxyl or benzyloxy.
Described has 1, cyclopentadiene (the S)-I and (S)-I ' of 1'-spirobindene alkane skeleton or (R)-I and (R)-I ', ethanol thallium, [Rh (C2H4) 2Cl] 2 mol ratio be 1:1:(1～1.2): (0.5～0.6), the temperature of reaction is between 25 DEG C to 80 DEG C, and the response time is 8 hours-48 hours.
In the inventive method, described organic solvent can be polarity or non-polar solven, such as benzene, carbon tetrachloride, oxolane, ether, dichloromethane, chloroform, toluene, dimethylbenzene, hexamethylene, normal hexane, normal heptane, dioxane, acetonitrile etc., it is recommended that solvent is benzene or oxolane.
The cyclopentadiene rhodium complex adopting the product spirocyclic ring scaffold of the inventive method gained can through recrystallization, and the method such as column chromatography is separated purification. As by the method for recrystallization, it is recommended that solvent is the mixed solvent of polar solvent and non-polar solven. The mixed solvents such as recommending solvent can be dichloromethane-normal hexane, isopropanol-petroleum ether, ethyl acetate-petroleum ether, ethyl acetate-normal hexane, isopropanol-ethyl acetate-petroleum ether. With column chromatography method, developing solvent used is polar solvent or non-polar solven, it is recommended that solvent can be petroleum ether, benzene, oxolane, ether.
Present invention also offers above-mentioned such as formula (S)-I, (S)-I ' or (R)-I, the preparation method of the cyclopentadiene compound of the 1,1'-spirobindene alkane skeleton shown in (R)-I '.
For compound (S)-I and (S)-I ', its preparation method comprises the steps: to react compound (S)-II with cyclopentadienyl sodium, carry out thermal rearrangement reaction subsequently, compound (S)-I and (S)-I ' can be obtained.
In above equation, solvents represents organic solvent;
For compound (R)-I and (R)-I ', its preparation method comprises the steps: to react compound (R)-II with cyclopentadienyl sodium, carry out thermal rearrangement reaction subsequently, compound (R)-I and (R)-I ' can be obtained.
In above equation, solvents represents organic solvent; Wherein, R1Same as above, X is arbitrarily selected from Cl, Br, I, OTs, OMs.
Formula (S)-I, (S)-I ' or (R)-I, (reaction condition and step are referred to Ye, B. to the conventional method that the preparation method of the compound shown in (R)-I ' is in this area this type of reaction; Cramer, N.J.Am.Chem.Soc.2013,135,636.). Particularly preferably following reaction condition in the present invention:
In oxolane, compound (R)-II or compound (S)-II is reacted with cyclopentadienyl sodium, carries out thermal rearrangement reaction subsequently, compound (R)-I and (R)-I ' can be obtained. React under suggestion argon shield. Specifically, in oxolane, 0 DEG C to 80 DEG C, have 1, (S)-II or (R)-II, sodium hydride, cyclopentadienyl sodium and the 15-crown-5 of 1'-spirobindene alkane skeleton react 12～24 hours, described reaction process can pass through this area conventional means (such as TLC or HPLC) and detect, as the terminal of reaction time generally using compound (R)-II or compound (S)-II disappearance; (the S)-II or (R)-II of the described 1,1'-of having spirobindene alkane skeleton, sodium hydride, cyclopentadienyl sodium, 15-crown-5 mol ratio be 1:(1～1.4): (1～1.4): 2; Subsequently, in organic solvent with 200-240 DEG C, carry out thermal rearrangement and react 16-36 hour;
Wherein, the volume mass of described oxolane and described compound (R)-II or compound (S)-II is 10～40mL/g than preferably.
Preparing compound (S)-I, (S)-I ' or (R)-I, in the method for (R)-I ', described reaction also includes last handling process after terminating. Described last handling process preferably includes following steps: add ammonium chloride saturated solution, and ether extracts three times, and anhydrous sodium sulfate dries, and filters, concentrating under reduced pressure or column chromatography.
Column chromatography gained compound, at organic solvent in (n-dodecane, toluene or dimethylbenzene etc.), is heated reaction, and temperature is preferably 220 DEG C～240 DEG C.
Wherein, the Molar of described n-dodecane, toluene or dimethylbenzene and column chromatography gained compound is 100～1000mL/mmol than preferably.
Described reaction terminate after last handling process, it is preferable that column chromatography.
In the present invention, described compound (S)-II or (R)-II
Wherein, R1Substituent group on C6～C16 aryl of H, F, Cl, Br, I, C1～C16 alkyl, C1～C6 perfluoroalkyl, C3～C16 cycloalkyl, C1～C16 alkoxyl, C7-C16 benzyloxy, C6～C16 aryl or replacement, C6～C16 aryl of described replacement is selected from fluorine, chlorine, bromine, iodine, C1～C16 alkoxyl, C1～C16 alkyl, C1～C16 fluoro-alkyl, nitro or amino.
Present invention also offers the above-mentioned preparation method of compound as shown in formula (S)-II or (R)-II.
For compound (S)-II, its preparation method includes following two kinds of methods:
Compound (S)-III is reacted with mesyl chloride (or paratoluensulfonyl chloride) through the effect of alkali in organic solvent and can obtain (S)-II.
Or by compound (S)-III, thionyl chloride, pyridine, react 24 hours to 48 hours, (S)-II can be obtained
For compound (R)-II, its preparation method comprises the steps:
By compound (R)-III in organic solvent, react through effect and the mesyl chloride (or paratoluensulfonyl chloride) of alkali and can obtain (R)-II. Specifically, in dichloromethane, 0 DEG C to 25 DEG C, there is benzylalcohol (the S)-III or (R)-III of 1,1'-spirobindene alkane skeleton, mesyl chloride (or paratoluensulfonyl chloride) and triethylamine and react 24 hours to 48 hours; The mol ratio of benzylalcohol (the S)-III or (R)-III of the described 1,1'-of having spirobindene alkane skeleton, mesyl chloride (or paratoluensulfonyl chloride) and triethylamine is 1:(2～6): (2～6);
Or in organic solvent, 25 DEG C to 80 DEG C, compound (R)-III, thionyl chloride, pyridine are reacted 24 hours to 48 hours, (R)-II can be obtained. Benzylalcohol (the S)-III or (R)-III of the described 1,1'-of having spirobindene alkane skeleton, thionyl chloride, pyridine mol ratio be 1:1:(5～10).
Wherein, R1Same as above, X is arbitrarily selected from Cl, Br, I, OTs, OMs.
The preparation method that present invention also offers the described compound as shown in formula (S)-III or (R)-III,
For compound (S)-III, its preparation method comprises the steps: to obtain compound (S)-IV in organic solvent under Hydro-Giene (Water Science)., 1,10-phenanthroline and cesium carbonate effect (S)-III.
Solvents represents organic solvent
For compound (R)-III, its preparation method comprises the steps: to obtain compound (S)-IV in organic solvent under Hydro-Giene (Water Science)., 1,10-phenanthroline and cesium carbonate effect (R)-III.
Solvents represents organic solvent
Wherein, R1Same as above.
In the inventive method, described organic solvent can be polar solvent. Such as methanol, ethanol, benzylalcohol, isopropanol, trifluoroethanol etc., it is recommended that solvent is methanol and benzylalcohol.
Described compound (S)-IV or (R)-IV Hydro-Giene (Water Science)., 1,10-phenanthroline, cesium carbonate mol ratio be 1:0.2:0.4:2.
Wherein, the temperature of described reaction is 80 DEG C of reactions 24 hours to 48 hours.
The preparation method that present invention also offers the described compound as shown in formula (S)-IV or (R)-IV,
For compound (S)-IV, its preparation method comprises the steps: to obtain compound (S)-V in organic solvent under the effect of DIBAL-H (S)-IV.
Solvents represents organic solvent
For compound (R)-IV, its preparation method comprises the steps: to obtain compound (R)-V in organic solvent under the effect of DIBAL-H (R)-IV.
Solvents represents organic solvent, and DIBAL-H represents diisobutyl aluminium hydride.
In the inventive method, described organic solvent can be polarity or non-polar solven. Such as benzene, toluene, carbon tetrachloride, oxolane, ether, dichloromethane, chloroform, toluene, dimethylbenzene, hexamethylene, normal hexane, normal heptane, dioxane, acetonitrile etc., it is recommended that solvent is benzene and toluene.
The mol ratio of described compound (S)-V or (R)-V, diisobutyl aluminium hydride is 1:(4～6).
Wherein, the temperature of described reaction is-78 DEG C and reacts 1～3 hour, reacts 1～5 hour under room temperature again.
Present invention also offers the described preparation method of compound as shown in formula (S)-V or (R)-V,
For compound (S)-V, its preparation method comprises the steps: 80 DEG C of reactions, compound (S)-VI can be obtained (S)-V with excessive thionyl chloride for 5～8 hours in methanol.
For compound (R)-V, its preparation method comprises the steps: 80 DEG C of reactions, compound (R)-VI can be obtained (R)-V with thionyl chloride for 5～8 hours in methanol.
Above-mentioned reaction advises post processing later: boil off unnecessary thionyl chloride, adds excessive methanol.
The preparation method that present invention also offers the described compound as shown in formula (S)-VI or (R)-VI,
For compound (S)-VI, its preparation method comprises the steps: by compound (S)-VII in organic solvent, can obtain compound (S)-VI through the effect of palladium and oxidant.
Solvent represents organic solvent, and oxidants represents oxidant
For compound (R)-VI, its preparation method comprises the steps: by compound (R)-VII in organic solvent, can obtain chemical combination (R)-VI through the effect of palladium compound and oxidant.
Pdsources represents that palladium compound, solvent represent organic solvent, and oxidants represents oxidant
In the inventive method, described organic solvent can be polarity or non-polar solven. Such as benzene, toluene, carbon tetrachloride, oxolane, ether, dichloromethane, chloroform, toluene, dimethylbenzene, hexamethylene, normal hexane, normal heptane, dioxane, acetonitrile, N, dinethylformamide, dimethyl sulfoxide etc., it is recommended that solvent is DMF and DMSO.
Wherein, described oxidant is iodine, iodobenzene acetate, potassium bromide, acetic acid iodine one or more;
Wherein, palladium compound is one or more in palladium, trifluoracetic acid palladium, Palladous chloride., two (acetylacetone,2,4-pentanedione) palladiums and allyl palladium chloride;
Wherein, alkali is triethylamine, sodium acetate, sodium benzoate, potassium acetate, pivalic acid sodium, one or more in pivalic acid caesium;
Described compound (S)-VII or the mol ratio of (R)-VII, alkali, palladium compound and oxidant are 1:(2.0～8.0): (0.01～0.4): (2.0～8.0);
The temperature of described reaction is 80～120 DEG C, it is advantageous to be 100～120 DEG C;
Present invention also offers described compound (S)-K and aoxidize Heck coupling reaction at asymmetric c h bond, build the application in the reaction of axial chirality compound.
It is also preferred that the left described application comprises the steps: in organic solvent, compound (S)-K and benzoyl peroxide first stir 30 minutes, add aryl-linking compound, alkene, Schweinfurt green and silver oxide reaction, can obtain compound O,
Wherein, described organic solvent is the various conventional organic solvent of this type of reaction of this area, it is advantageous to be methanol.
Wherein, described aryl-linking compound, alkene, compound (S)-K, the mol ratio of benzoyl peroxide, Schweinfurt green and silver oxide is 1:(1.0～2.0): (0.05～0.1): (0.05～0.1): (0.02～1.0): (1.0～2.0).
Wherein, described compound (S)-K is preferably
The temperature of described asymmetric c h bond priming reaction is 25～80 DEG C, it is advantageous to be 25～45 DEG C.
Provided by the present invention based on spiral shell chiral skeleton cyclopentadiene compounds and its rhodium compound, it is possible to be applied in the c h bond priming reaction of metal rhodium catalysis, outstanding productivity, regioselectivity, enantioselectivity can be obtained. Can be applied on more complicated substrate, expand the use scope of this type of reaction greatly.
Detailed description of the invention
Be will assist in by following embodiment and understand the present invention, but be not limiting as present disclosure.
Embodiment 1: based on the synthesis of spiral shell chirality cyclopentadiene compound (S)-K1:
(S) synthesis of-VI-1: under argon shield, in the tube sealing of 100mL, adds (S)-VII (0.92g, 3mmol), Pd (OAc)2(134.7mg, 0.6mmol), iodobenzene acetate (2.42g, 7.5mmol), iodine (1.9g, 7.5mmol) and DMF (30mL), stirring and dissolving, heating, to 100 DEG C, is stirred 36 hours. Reaction is cooled to room temperature, removal of solvent under reduced pressure, uses saturated Na2SO3(30mL) cancellation, is acidified to acidity with 1NHCl (30mL) subsequently, extracts anhydrous Na with DCM2SO4Dry. Filtering, decompression is distilled off solvent, and crude product passes through column chromatography for separation (petrol ether/ethyl acetate/acetic acid: 4/1/0.01).
White solid, 70% yield (yield), m.p. > 300 DEG C.1HNMR(400MHz,DMSO-d6) δ 8.19 (d, J=8.0Hz, 2H), 7.56 (d, J=8.0Hz, 2H), 3.48-3.35 (m, 4H), 2.95-2.87 (m, 2H), 2.80-2.69 (m, 2H);13CNMR(100MHz,DMSO-d6) δ 169.4,146.3,145.1,138.1,138.0,127.2,91.5,62.7,39.4,30.1; IR (thin film): νmax(cm-1)=2956,2924,2853,1749,1663,1450,1328,1261,808; HRMS (ESI) value of calculation C19H18I2NO4[M+NH4]+: 577.932; Measured value: 577.9319; [α]D 28=-15.2 (c=0.10, methanol).
(S) synthesis of-V-1: under argon shield, in two mouthfuls of bottles of 100mL, adds (S)-VI-1 (100mg, 0.178mmol), adds thionyl chloride (2mL) stirring and dissolving, and heating, to 80 DEG C, is stirred 8 hours. Reaction is cooled to room temperature, and decompression removes excessive thionyl chloride, adds methanol (1mL), and heating, to 80 DEG C, is stirred 4 hours, is cooled to room temperature. Decompression is distilled off solvent, and crude product passes through column chromatography for separation (petrol ether/ethyl acetate: 40/1).
White solid, 95% yield (yield), m.p.=143-144 DEG C.1HNMR(400MHz,CDCl3) δ 7.66 (d, J=8.0Hz, 2H), 7.00 (d, J=8.0Hz, 2H), 3.24 (s, 6H), 3.05-2.87 (m, 4H), 2.64-2.56 (m, 2H), 2.24-2.18 (m, 2H);13CNMR(100MHz,CDCl3) δ 167.7,147.2,145.2,137.9,136.2,127.1,90.3,62.6,51.3,39.7,30.2; IR (thin film): νmax(cm-1)=2942,2923,2872,1721,1567,1429,1279,1250,798; HRMS (ESI) value of calculation C21H22I2NO4[M+NH4]+: 605.9633; Measured value: 605.9633; [α]D 26=-299.2 (c=0.20, chloroforms).
(S) synthesis of-IV-1: under argon shield; in the Schlenk pipe of 20mL; add (S)-V-1 (99.5mg; 0.17mmol); add toluene (2mL) stirring and dissolving; it is cooled to-78 DEG C, adds diisobutyl aluminum hydrogen (1.5M toluene solution, 0.68mL) and stir 3 hours. Subsequently, recover to room temperature reaction 5 hours. Use saturated NH4Cl (5mL) cancellation, is extracted with ethyl acetate, anhydrous Na2SO4Dry. Filtering, decompression is distilled off solvent, and crude product passes through column chromatography for separation (petrol ether/ethyl acetate: 5/1).
White solid, 93% yield (yield), m.p.=164-165 DEG C.1HNMR(400MHz,CDCl3) δ 7.74 (d, J=8.0Hz, 2H), 6.94 (d, J=8.0Hz, 2H), 4.39 (d, J=12.0Hz, 2H), 4.20 (d, J=12.0Hz, 2H), 3.37 (s, 2H), 3.06-2.82 (m, 4H), 2.31-2.26 (m, 2H), 2.04-1.95 (m, 2H);13CNMR(100MHz,CDCl3) δ 150.1,143.9,139.2,137.9,126.5,100.4,63.0,40.0,30.1; IR (thin film): νmax(cm-1)=3226,2951,2935,2878,2843,1406,1003,809; Elementary analysis value of calculation C19H18I2O2: C, 42.88; H, 3.41; Measured value: C, 42.92; H, 3.47; [α]D 27=-239.0 (c=0.20, chloroforms).
(S) synthesis of-III-1: under argon shield, in the tube sealing of 20mL, adds (S)-IV-1 (532.2mg; 1mmol), Hydro-Giene (Water Science). (38.1mg, 0.2mmol) is added; 1; 10-phenanthroline (72.1mg, 0.4mmol), cesium carbonate (912.2mg; 2.8mmol); adding methanol (5mL) stirring and dissolving, heating, to 80 DEG C, is reacted 37 hours. Being cooled to room temperature, filtered through silica gel, decompression is distilled off solvent, and crude product passes through column chromatography for separation (petrol ether/ethyl acetate: 1/1).
White solid, 81% yield (yield), m.p.=202-204 DEG C.1HNMR(400MHz,CDCl3) δ 7.16 (d, J=8.4Hz, 2H), 6.80 (d, J=8.4Hz, 2H), 4.39 (d, J=12.0Hz, 2H), 4.29 (d, J=12.0Hz, 2H), 3.86 (s, 6H), 3.48 (s, 2H), 2.92-2.91 (m, 4H), 2.30-2.28 (m, 2H), 2.00-1.92 (m, 2H);13CNMR(100MHz,CDCl3) δ 158.5,149.2,135.2,124.5,109.7,61.7,56.6,55.8,40.2,29.6; IR (thin film): νmax(cm-1)=3483,3384,2928,1592,1476,1461,1253,978,787; Elementary analysis value of calculation C21H24O4: C, 74.09; H, 7.11; Measured value: C, 73.91; H, 7.27; [α]D 26=-89.8 (c=0.20, chloroforms).
Water white oil, 64% yield (yield).1HNMR(400MHz,CDCl3) δ 7.42-7.40 (m, 4H), 7.37-7.33 (m, 4H), 7.30-7.27 (m, 2H), 7.12 (d, J=8.4Hz, 2H), 6.84 (d, J=8.4Hz, 2H), 5.14 (d, J=12.0Hz, 2H), 5.07 (d, J=12.0Hz, 2H), 4.42 (d, J=12.0Hz, 2H), 4.31 (d, J=12.0Hz, 2H), 3.38 (s, 2H), 2.93-2.89 (m, 4H), 2.33-2.27 (m, 2H), 2.04-1.95 (m, 2H);13CNMR(100MHz,CDCl3) δ 157.6,149.4,137.0,135.7,128.5,127.8,127.2,125.1,124.5,11 1.4,70.5,61.7,56.8,40.2,29.7; IR (thin film): νmax(cm-1)=3564,3394,2941,1592,1453,748; HRMS (EI) value of calculation C33H32NaO4[M+Na]+: 515.2193; Measured value: 515.2192; [α]D 29=-146.2 (c=0.15, chloroforms).
(S) synthesis of-II-1: under argon shield; in the tube sealing of 20mL; add (S)-III-1 (368mg; 1.08mmol); add pyridine (87 μ L, 1.08mmol), add chloroform (10mL); adding the chloroformic solution (5mL) of thionyl chloride (780 μ L), at 0 DEG C, then stirring is heated to reflux 40 hours in 30 minutes. Being cooled to room temperature, the cancellation that adds water is reacted, and chloroform extracts three times, saturated NaHCO3 washs once, and saturated nacl aqueous solution washs once, and anhydrous sodium sulfate dries, filtering, decompression is distilled off solvent, and crude product passes through column chromatography for separation (petroleum ether/dichloromethane/ethyl acetate: 100/2/1).
White solid, 86% yield (yield), m.p.=202-204 DEG C.1HNMR(400MHz,CDCl3) δ 7.23 (d, J=8.0Hz, 2H), 6.83 (d, J=8.0Hz, 2H), 4.38 (d, J=10.8Hz, 2H), 4.17 (d, J=10.8Hz, 2H), 3.88 (s, 6H), 3.00-2.96 (m, 4H), 2.41-2.31 (m, 4H);13CNMR(100MHz,CDCl3) δ 158.0,149.1,135.6,125.8,122.1,110.4,62.3,56.1,39.2,38.4,29.8; IR (thin film): νmax(cm-1)=3005,2939,1589,1286,1087,807; HRMS (EI) value of calculation C21H22O2Cl2[M]+: 376.0997; Measured value: 376.1002; [α]D 28=-145.0 (c=0.2, chloroforms).
(S) synthesis of-I-1 and (S)-I '-1: under argon shield; in the tube sealing of 20mL; add sodium hydrogen (16.8mg; 0.42mmol); add oxolane (1mL); tetrahydrofuran solution (the 0.21mL of sodium cyclopentadiene; 0.42mmol); it is subsequently added (S)-I-1 (113.2mg; tetrahydrofuran solution (2mL) 0.3mmol); add 15-crown-5 (132.2 μ L, 0.6mmol), stir 48 hours at 80 DEG C. It is cooled to room temperature, saturated NH4Cl cancellation is reacted, and ether extracts three times, and anhydrous sodium sulfate dries, and filters, and decompression is distilled off solvent, and crude product passes through column chromatography for separation (petrol ether/ethyl acetate: 100/1). Subsequently mixture is dissolved in n-dodecane (30mL), degassed three times, 240 DEG C of oil baths is reacted 15 hours. Being cooled to room temperature, product passes through column chromatography for separation (petrol ether/ethyl acetate: 100/1).
White solid, 90% liang of step total recovery (yield), (S)-I-1:(S)-I '-1=1.3:1.1HNMR(400MHz,CDCl3) δ 7.13-7.11 (m, 2H), 6.79-6.75 (m, 2H), 6.50 (d, J=4.8Hz, 0.43H), 6.15-6.12 (m, 1.57H), 3.78-3.75 (m, 7H), 3.61-3.56 (m, 1H), 3.45 (d, J=13.2Hz, 1H), 3.38-3.29 (m, 1H), 3.12-2.75 (m, 6H), 2.45-2.25 (m, 2H), 2.13-2.05 (m, 2H);13CNMR(100MHz,CDCl3) δ 157.5,156.5,156.4,148.8,148.6,144.4,141.0,139.0,138.5,134.7,134.24,134.19,128.7,127.5,124.0,123.2,122.73,122.65,122.0,121.9,110.0,109.7,109.2,62.1,61.5,55.9,55.3,47.1,39.2,39.1,38.8,38.1,29.4,29.2,26.4,24.4,24.0; IR (thin film): νmax(cm-1)=2947,2922,2850,1602,1476,1459,1251,1082,797; HRMS (EI) value of calculation C26H26O2[M]+: 370.1933; Measured value: 370.1924; [α]D 27=156.9 (c=0.20, chloroforms).
(S) synthesis of-K1: under argon shield; in the tube sealing of 20mL; add (S)-I-1 and (S)-I '-1 (198mg; 287 μm of ol); add degassed benzene (1mL); the tetrahydrofuran solution (0.21mL, 0.36mmol) of ethanol thallium, at 80 DEG C, lucifuge stirs 16 hours. It is cooled to room temperature, adds [Rh (C2H4)2Cl]2(70mg, 0.18mmol), stirs 24 hours under room temperature. Kieselguhr and neutral alumina filter, and benzene washs, and removal of solvent under reduced pressure can obtain complex (S)-K1.
Yellow solid, 74% yield (yield) m.p.=181-183 DEG C, decomposes.1HNMR(400MHz,C6D6) δ 7.04 (d, J=8.4Hz, 1H), 6.96 (d, J=8.0Hz, 1H), 6.60 (d, J=8.4Hz, 1H), 6.45 (d, J=8.0Hz, 1H), 5.74 (s, 1H), 4.60 (s, 1H), 4.55 (t, J=2.4Hz, 1H), 3.91 (d, J=13.6Hz, 1H), 3.56 (s, 3H), 3.44 (d, J=13.6Hz, 1H), 3.33 (s, 3H), 3.29 (d, J=12.8Hz, 1H), 3.10 (d, J=12.8Hz, 1H), 2.91 (t, J=9.6Hz, 2H), 2.81-2.72 (m, 2H), 2.65-2.59 (m, 2H), 2.13 (t, J=9.6Hz, 2H), 2.08-1.91 (m, 4H), 1.21 (t, J=9.6Hz, 2H), 0.89 (t, J=9.6Hz, 2H),13CNMR(151MHz,C6D6) δ 158.5,157.5,149.1,149.0,134.8,133.5,125.8,123.3, (123.2,123.1,111.0 d, J=4.4Hz), (110.0,109.1,97.6 d, J=3.6Hz), (91.3 d, J=8.0Hz), 89.4 (d, J=4.2Hz), 83.0 (d, J=4.4Hz), 62.6,55.4,55.2, (39.8 d, J=17.7Hz), 39.7, (39.4,37.0 d, J=13.7Hz), 29.4,24.0,21.9;IR (thin film): νmax(cm-1)=3054,2923,2849,1590,1461,1281,1015,791; HRMS (MALDI-FT_DHB) value of calculation C26H26O2Rh[M-2(C2H4)+H]+: 473.0982; Measured value: 473.0985; [α]D 28=-127.9 (c=0.20, dichloromethane).
Yellow solid, 71% yield (yield) m.p.=181-183 DEG C, decomposition .HRMS (MALDI-FT_DHB) value of calculation C26H26O2Rh [M-2 (C2H4)+H]+: 473.0982; Measured value: 473.0984; [α] D28=+126.9 (c=0.20, dichloromethane).
Yellow foaming material, 73% yield (yield) .1HNMR (400MHz, C6D6) δ 7.47 (d, J=7.6Hz, 2H), 7.28 (d, J=7.6Hz, 2H), 7.21 (t, J=7.6Hz, 2H), 7.15-7.06 (m, 4H), 7.03 (d, J=8.0Hz, 1H), 6.95 (d, J=8.0Hz, 1H), 6.68 (d, J=8.0Hz, 1H), 6.54 (d, J=8.0Hz, 1H), 5.65 (br, 1H), 4.97 (d, J=12.0Hz, 1H), 4.88 (d, J=12.0Hz, 1H), 4.71 (br, 1H), 4.67 (dd, J=15.2Hz, 12.0Hz, 2H), 4.32 (t, J=2.8Hz, 1H), 4.07 (d, J=13.6Hz, 1H), 3.54 (d, J=13.6Hz, 1H), 3.40 (d, J=12.8Hz, 1H), 3.13 (d, J=13.2Hz, 1H), 2.84-2.58 (m, 6H), 2.13-1.94 (m, 6H), 1.15 (br, 2H), 0.79 (br, 2H),13CNMR(100MHz,C6D6) δ 157.6,156.6,149.13,149.09,138.6,137.8,134.9,133.7,128.6,128.5,127.9,127.6,127.0,126.6,123.4,123.2,123.1,111.9 (d, J=4.2Hz), 111.2,110.7,97.0 (d, J=3.8Hz), 91.7 (d, J=3.5Hz), 89.6 (d, J=4.2Hz), 82.6 (d, J=4.2Hz), 70.4, (69.9,62.7,40.1 d, J=14.7Hz), (39.9,39.1,37.5 d, J=17.6Hz), 30.2,29.4,24.1,22.3; IR (thin film): νmax(cm-1)=3055,2924,2851,1588,1497,1474,1260,1104,803,695; HRMS (MALDI-FT_DHB) value of calculation C38H33O2Rh[M-2(C2H4)+H]+: 624.1530; Measured value: 624.1531; [α]D 28=-223.2 (c=0.20, dichloromethane).
Yellow foaming material, 71% yield (yield) .HRMS (MALDI-FT_DHB) value of calculation C38H33O2Rh [M-2 (C2H4)+H]+: 624.150; Measured value: 624.1521; [α] D28=+222.2 (c=0.20, dichloromethane).
Yellow solid, 73% yield (yield), m.p. > 300 DEG C of .1HNMR (400MHz, C6D6) δ 7.02 (d, J=8.4Hz, 1H), 7.00 (d, J=8.0Hz, 1H), 6.72 (d, J=8.4Hz, 1H), 6.51 (d, J=8.4Hz, 1H), 5.88 (br, 1H), 4.76 (br, 1H), 4.43 (t, J=2.4Hz, 1H), 4.30-4.24 (m, 1H), 4.22-4.16 (m, 1H), 3.91 (d, J=13.4Hz, 1H), 3.47 (d, J=13.2Hz, 1H), 3.39 (d, J=13.2Hz, 1H), 3.13 (d, J=12.8Hz, 1H), 2.88 (br, 2H), 2.81-2.70 (m, 2H), 2.66-2.59 (m, 2H), 2.20 (br, 2H), 2.10-1.89 (m, 4H), 1.40 (d, J=6.0Hz, 3H), 1.33 (br, 2H), 1.16-1.10 (m, 9H), 0.92 (br, 2H),13CNMR(100MHz,C6D6) δ 157.3,155.3,149.33,149.29,134.1,133.5,128.6,123.5,123.4,123.2,113.5,112.4 (d, J=4.2Hz), 111.4,97.2 (d, J=3.8Hz), (91.7 d, J=3.5Hz), 89.5 (d, J=4.4Hz), (81.9 d, J=4.4Hz), 70.9,69.1, (62.9,40.0,39.9 d, J=10.3Hz), (39.1,38.2 d, J=10.6Hz), 29.5,29.4,24.2,23.3,22.6,22.2,22.1;IR (thin film): νmax(cm-1)=3054,2964,2927,1587,1469,1432,1381,1259,1117,806; HRMS (MALDI-FT_DHB) value of calculation C30H34O2Rh[M-2(C2H4)+H]+: 529.1608; Measured value: 529.1608; [α]D 25=-284.5 (c=0.20, dichloromethane).
Yellow solid, 75% yield (yield), m.p. > 300 DEG C of .HRMS (MALDI-FT_DHB) value of calculation C30H34O2Rh [M-2 (C2H4)+H]+: 529.168; Measured value: 529.1618; [α] D25=+285.5 (c=0.20, dichloromethane).
Yellow solid, 67% yield (yield), m.p.=127-128 DEG C.1HNMR(400MHz,C6D6) δ 7.59 (d, J=7.2Hz, 1H), 7.26 (t, J=7.6Hz, 1H), 7.10-7.02 (m, 2H), 6.99 (d, J=6.8Hz, 1H), 6.89 (d, J=7.2Hz, 1H), 5.14 (br, 1H), 4.69 (t, J=2.4Hz, 1H), 4.07 (br, 1H), 3.45 (d, J=14.0Hz, 1H), 3.07 (dd, J=13.2, 6.4Hz, 2H), 2.91-2.86 (m, 2H), 2.81-2.73 (m, 2H), 2.67-2.59 (m, 2H), 2.49 (d, J=13.2Hz, 1H), 2.08-1.79 (m, 6H), 1.34-1.21 (m, 2H), 0.97-0.88 (m, 2H),13CNMR(100MHz,C6D6) δ 147.7,147.3,143.2,141.8,138.1,134.5,132.6,128.8,127.5,123.1,123.07,111.3 (d, J=4.8Hz), 101.0 (d, J=3.7Hz), 89.8 (d, J=3.8Hz), (89.0 d, J=4.0Hz), 83.6 (d, J=4.1Hz), 61.6, (41.5 d, J=12.3Hz), 39.3,38.8,36.7 (d, J=13.5Hz), 30.4,30.3,30.2,27.2; IR (thin film): νmax(cm-1)=3048,2983,2949,2837,1593,1429,755; Elementary analysis value of calculation C28H29Rh:C, 71.79; H, 6.24; Measured value: C, 72.22; H, 6.36; [α]D 29=-172.4 (c=0.20, chloroforms).
Yellow solid, 70% yield (yield), MS (MALDI-FT_DHB) C26H26Rh[M-2(C2H4)+H]+: 440.1011; Measured value: 440.1021.
Yellow solid, 72% yield (yield), MS (MALDI-FT_DHB) C26H19F6Rh[M-2(C2H4)+H]+: 548.0446; Measured value: 548.0436.
Application Example 2:
General reactions operates: under nitrogen protection, (S)-K1 (5.3mg, 10 μm of ol) and benzoyl peroxide (2.4mg, 10 μm of ol) are dissolved in methanol (0.5mL), reacts 30min under room temperature. Sequentially add M (0.2mmol), N (0.24mmol), Schweinfurt green (7.3mg, 0.04mmol), Ag2CO3(55.2mg, 0.2mmol), methanol (0.5mL), reacts at 25 DEG C. TLC follows the tracks of after reacting completely, and uses saturated sodium bicarbonate solution cancellation, dichloromethane extraction, and anhydrous sodium sulfate dries, and filters removal of solvent under reduced pressure, and column chromatography purifies (petroleum ether/acetone=30/1). The ee value of product is measured by HPLC.
O-1:
92% yield (yield).1HNMR(400MHz,CDCl3) δ 8.94 (d, J=4.8Hz, 1H), 8.11-8.04 (m, 2H), 8.01-7.73 (m, 5H), 7.67-7.52 (m, 5H), 7.42-7.32 (m, 4H), 7.24 (s, 1H), 7.21-7.13 (m, 1H), 7.13-6.93 (m, 3H), 6.77 (d, J=16.4Hz, 1H); [chiral column DaicelChiralcelAD-H (0.46cmx25cm), normal hexane/isopropanol=90/10, v=1.0mL min-1, detection wavelength=254nm, t (minor)=20.96min, t (major)=46.04min], 95:5er; [α]D 22=+560.1 (c=0.22, chloroforms).
O-2:
80% yield (yield).1HNMR(400MHz,CDCl3) δ 8.92 (d, J=5.2Hz, 1H), 8.35 (d, J=8.4Hz, 1H), 7.96 (d, J=8.8Hz, 1H), 7.90-7.76 (m, 3H), 7.71 (d, J=8.8Hz, 1H), 7.67-7.64 (m, 2H), 7.54-7.53 (m, 2H), 7.45-7.31 (m, 5H), 7.21-7.17 (m, 2H), 7.13-7.00 (m, 3H), 6.78 (d, J=16.4Hz, 1H), 4.23 (s, 3H);[chiral column DaicelChiralpakID-3 (0.46cmx15cm), normal hexane/isopropanol=70/30, v=0.7mL min-1, detection wavelength=214nm, t (minor)=11.18min, t (major)=16.53min], 97:3er; [α]D 28=+485.5 (c=0.20, chloroforms).
O-3:
92% yield (yield).1HNMR(400MHz,CDCl3) δ 8.92 (d, J=5.2Hz, 1H), 8.07 (d, J=8.4Hz, 1H), 8.01-7.92 (m, 2H), 7.89-7.84 (m, 2H), 7.80 (d, J=7.2Hz, 1H), 7.67-7.64 (m, 3H), 7.54-7.52 (m2H), 7.47-7.41 (m, 1H), 7.39-7.32 (m, 3H), 7.24 (d, J=2.0Hz, 1H), 7.20-7.17 (m, 1H), 7.13-7.00 (m, 3H), 6.74 (d, J=16.4Hz, 1H), 2.90 (s, 3H); [chiral column DaicelChiralcelAD-H (0.46cmx25cm), normal hexane/isopropanol=90/10, v=1.0mL min-1, detection wavelength=254nm, t (minor)=14.86min, t (major)=44.71min], 92:8er; [α]D 27=+507.9 (c=0.20, chloroforms).
O-3:
97% yield (yield).1HNMR(400MHz,CDCl3) δ 8.93 (d, J=5.2Hz, 1H), 8.20 (d, J=8.4Hz, 1H), 8.00 (d, J=8.8Hz, 1H), 7.92 (d, J=5.2Hz, 1H), 7.88 (d, J=8.8Hz, 1H), 7.83 (d, J=8.0Hz, 1H), 7.78 (d, J=12.0Hz, 1H), 7.68-7.66 (m, 2H), 7.59 (d, J=8.8Hz, 1H), 7.55-7.53 (m, 2H), 7.50-7.45 (m, 1H), 7.44-7.33 (m, 3H), 7.26-7.19 (m, 2H), 7.12-7.05 (m, 3H), 6.72 (dd, J=16.0,1.6Hz, 1H); [chiral column DaicelChiralcelAD-H (0.46cmx25cm), normal hexane/isopropanol=90/10, v=1.0mL min-1, detection wavelength=254nm, t (minor)=15.00min, t (major)=34.03min], 95:5er; [α]D 27=+495.0 (c=0.20, chloroforms).
O-4:
Yellow foaming material, 85% yield (yield).1HNMR(400MHz,CDCl3) δ 8.84 (d, J=5.2Hz, 1H), 7.92 (d, J=8.8Hz, 1H), 7.86 (d, J=8.8Hz, 1H), 7.78 (d, J=7.6Hz, 1H), 7.73-7.69 (m, 2H), 7.64-7.55 (m, 3H), 7.61-7.57 (m, 4H), 7.34-7.22 (m, 3H), 7.15-7.04 (m, 2H), 6.96 (d, J=8.0Hz, 1H), 6.67 (d, J=16.4Hz, 1H), 3.47 (s, 3H);13CNMR(100MHz,CDCl3) δ 156.8,155.1,144.0,137.6,136.7,134.6,133.2,133.0,132.7,132.1,132.0,130.4,129.8,129.4,128.8,127.8,127.7,127.4,127.1,126.7,126.6,126.3,126.0,125.95,125.66,125.64,125.5,123.2,121.2,118.5,110.6,55.7; IR (thin film): νmax(cm-1)=3053,2968,2928,1626,1586,1467,1256,1070,747; HRMS (ESI) value of calculation C32H24NO[M+H]+: 438.1852; Measured value: 438.1852; [chiral column DaicelChiralpakID-3 (0.46cmx15cm), normal hexane/isopropanol=70/30, v=0.7mL min-1, detection wavelength=254nm, t (minor)=6.89min, t (major)=11.25min], 97:3er; [α]D 29=+416.6 (c=1.0, chloroforms).
O-5:
19% yield (yield).1HNMR(400MHz,CDCl3) δ 8.09 (d, J=8.4Hz, 1H), 8.04 (d, J=8.8Hz, 1H), 7.93-7.90 (m, 2H), 7.79-7.73 (m, 3H), 7.67-7.65 (m, 2H), 7.58-7.48 (m, 2H), 7.42-7.31 (m, 5H), 7.24 (d, J=16.4Hz, 1H), 7.20.7.16 (m, 1H), 7.11-7.09 (m, 2H), 7.01-6.97 (m, 1H), 6.78 (d, J=16.0Hz, 1H), 2.82 (s, 3H);[chiral column DaicelChiralpakIE-3 (0.46cmx25cm), normal hexane/isopropanol=80/20, v=0.7mL min-1, detection wavelength=254nm, t (minor)=13.25min, t (major)=14.13min], 97:3er; [α]D 28=+396.7 (c=0.40, chloroforms).
O-6:
Yellow solid, m.p.=193-195 DEG C, 79% yield (yield).1HNMR(400MHz,CDCl3) δ 8.81 (d, J=5.6Hz, 1H), 8.07 (d, J=8.8Hz, 1H), 8.01 (d, J=8.8Hz, 1H), 7.96 (d, J=8.0Hz, 1H), 7.90 (d, J=8.0Hz, 1H), 7.83 (d, J=5.6Hz, 1H), 7.73-7.63 (m, 3H), 7.59-7.57 (m, 2H), 7.47-7.33 (m, 5H), 7.30-7.23 (m, 2H), 7.18 (dd, J=8.8,1.6Hz, 1H), 7.03 (d, J=8.4Hz, 1H), 6.76 (d, J=16.4Hz, 1H);13CNMR(100MHz,CDCl3) δ 159.6,142.7,136.1,134.9,134.7,133.7,133.4,133.1,132.9,13 2.8,130.4,128.88,128.86,128.0,127.9,127.87,127.6,127.5,127.4,126.9,126.8,126.6,126.3,126.2,125.8,123.2,122.7,120.3; IR (thin film): νmax(cm-1)=3047,3019,2924,2852,1695,1682,1620,1584,1557,1507,1497,8 48,742; HRMS (ESI) value of calculation C31H22N[M+H]+: 408.1747; Measured value: 408.1749; [chiral column DaicelChiralcelAD-H (0.46cmx25cm), normal hexane/isopropanol=90/10, v=1.0mL min-1, detection wavelength=254nm, t (minor)=31.21min, t (major)=44.37min], 79:21er; [α]D 27=+254.1 (c=0.20, chloroforms).
O-7:
56% yield (yield).1HNMR(400MHz,CDCl3) δ 8.89 (d, J=5.2Hz, 1H), 8.34 (d, J=8.0Hz, 1H), 7.95 (d, J=8.8Hz, 1H), 7.86-7.77 (m, 3H), 7.68 (d, J=8.8Hz, 1H), 7.41-7.35 (m, 2H), 7.33 (s, 1H), 7.20-7.15 (m, 1H), 7.14-6.99 (m, 8H), 6.67 (d, J=16.4Hz, 1H), 4.20 (s, 3H); [chiral column DaicelChiralpakID-3 (0.46cmx15cm), normal hexane/isopropanol=80/20, v=0.7mL min-1, detection wavelength=254nm, t (minor)=15.88min, t (major)=17.45min], 96:4er; [α]D 27=+480.0 (c=0.20, chloroforms).
O-8:
48% yield (yield).1HNMR(400MHz,CDCl3) δ 8.89 (d, J=5.2Hz, 1H), 8.33 (d, J=8.4Hz, 1H), 7.95 (d, J=8.8Hz, 1H), 7.88-7.76 (m, 3H), 7.68 (d, J=8.8Hz, 1H), 7.43-7.34 (m, 2H), 7.33 (s, 1H), 7.20-7.13 (m, 3H), 7.09-6.96 (m, 5H), 6.62 (d, J=16.4Hz, 1H), 4.20 (s, 3H), 1.20 (s, 9H); [chiral column DaicelChiralpakID-3 (0.46cmx15cm), normal hexane/isopropanol=85/15, v=0.7mL min-1, detection wavelength=254nm, t (minor)=16.58min, t (major)=19.12min], 97:3er; [α]D 27=+485.0 (c=1.00, chloroforms).
O-9:
61% yield (yield).1HNMR(400MHz,CDCl3) δ 8.89 (d, J=5.2Hz, 1H), 8.32 (d, J=8.4Hz, 1H), 7.95 (d, J=8.8Hz, 1H), 7.86-7.76 (m, 3H), 7.69 (d, J=8.8Hz, 1H), 7.39-7.31 (m, 2H), 7.31 (s, 1H), 7.18-7.14 (m, 1H), 7.09-6.94 (m, 5H), 6.66 (d, J=8.8Hz, 2H), 6.53 (d, J=16.0Hz, 1H), 4.19 (s, 3H), 3.69 (s, 3H); [chiral column DaicelChiralpakID-3 (0.46cmx15cm), normal hexane/isopropanol=90/10, v=1.0mL min-1, detection wavelength=254nm, t (minor)=20.13min, t (major)=27.83min], 96:4er;[α]D 26=+556.9 (c=1.00, chloroforms).
O-10:
67% yield (yield).1HNMR(400MHz,CDCl3) δ 8.89 (d, J=5.2Hz, 1H), 8.37 (d, J=8.0Hz, 1H), 7.97 (d, J=8.8Hz, 1H), 7.89-7.79 (m, 3H), 7.57 (d, J=8.8Hz, 1H), 7.50-7.35 (m, 2H), 7.25-7.19 (m, 2H), 7.12 (d, J=8.0Hz, 1H), 7.09-7.04 (m, 1H), 6.95 (d, J=16.8Hz, 1H), 6.85 (d, J=16.8Hz, 1H), 4.22 (s, 3H);19FNMR(376Hz,CDCl3) δ-143.0 (m) ,-156.7 (m) ,-163.2 (m); [chiral column DaicelChiralpakID-3 (0.46cmx15cm), normal hexane/isopropanol=70/30, v=0.7mL min-1, detection wavelength=254nm, t (minor)=5.75min, t (major)=7.72min], 94:6er; [α]D 27=+376.3 (c=1.00, chloroforms).
O-11:
96% yield (yield).1HNMR(400MHz,CDCl3) δ 8.86 (d, J=5.2Hz, 1H), 8.35 (d, J=8.4Hz, 1H), 7.94 (d, J=8.8Hz, 1H), 7.88-7.71 (m, 3H), 7.51-7.37 (m, 3H), 7.29-7.17 (m, 3H), 7.05-7.01 (m, 2H), 6.39 (d, J=15.6Hz, 1H), 4.14 (s, 3H), 4.02 (q, J=7.2Hz, 2H), 1.13 (t, J=7.2Hz, 3H); [chiral column DaicelChiralpakID-3 (0.46cmx15cm), normal hexane/isopropanol=80/20, v=0.7mL min-1, detection wavelength=254nm, t (major)=17.85min, t (minor)=21.75min], 97:3er; [α]D 22=+292.6 (c=1.00, chloroforms).
O-11:
91% yield (yield).1HNMR(400MHz,CDCl3) δ 8.86 (d, J=5.2Hz, 1H), 8.34 (d, J=8.4Hz, 1H), 7.96 (d, J=8.8Hz, 1H), 7.86-7.80 (m, 3H), 7.50-7.37 (m, 3H), 7.29 (d, J=15.6Hz, 1H), 7.22-7.14 (m, 2H), 7.05-6.99 (m, 2H), 6.39 (d, J=15.6Hz, 1H), 4.15 (s, 3H), 3.56 (s, 3H); [chiral column DaicelChiralpakID-3 (0.46cmx15cm), normal hexane/isopropanol=70/30, v=0.7mL min-1, detection wavelength=254nm, t (major)=12.51min, t (minor)=14.69min], 96:4er; [α]D 27=+290.6 (c=1.00, chloroforms).
O-12:
70% yield (yield).1HNMR(400MHz,CDCl3) δ 8.87 (d, J=5.2Hz, 1H), 8.34 (d, J=8.4Hz, 1H), 7.95 (d, J=8.8Hz, 1H), 7.88-7.76 (m, 3H), 7.53-7.34 (m, 3H), 7.25-7.15 (m, 3H), 7.08-6.98 (m, 2H), 6.32 (d, J=15.6Hz, 1H), 4.15 (s, 3H), 1.32 (s, 9H); [chiral column DaicelChiralpakID-3 (0.46cmx15cm), normal hexane/isopropanol=80/20, v=0.7mL min-1, detection wavelength=254nm, t (major)=9.29min, t (minor)=11.71min], 97:3er; [α]D 29=+301.5 (c=1.00, chloroforms).
O-13:
58% yield (yield).1HNMR(400MHz,CDCl3) δ 8.86 (d, J=5.2Hz, 1H), 8.35 (d, J=8.4Hz, 1H), 7.95 (d, J=8.8Hz, 1H), 7.89-7.76 (m, 3H), 7.51-7.36 (m, 3H), 7.33-7.28 (m, 4H), 7.25-7.12 (m, 4H), 7.05-7.01 (m, 2H), 6.44 (d, J=15.6Hz, 1H), 5.00 (s, 2H), 4.14 (s, 3H); [chiral column DaicelChiralpakID-3 (0.46cmx15cm), normal hexane/isopropanol=65/25, v=0.7mL min-1, detection wavelength=254nm, t (major)=13.55min, t (minor)=16.07min], 96:4er; [α]D 32=+292.6 (c=1.00, chloroforms).
O-14:
68% yield (yield).1HNMR(400MHz,CDCl3) δ 8.88 (d, J=4.8Hz, 1H), 8.37 (d, J=8.4Hz, 1H), 7.95 (d, J=8.8Hz, 1H), 7.87-7.64 (m, 7H), 7.61 (d, J=8.4Hz, 1H), 7.46-7.30 (m, 5H), 7.24-7.17 (m, 2H), 7.15-7.01 (m, 3H), 6.69 (d, J=16.0Hz, 1H), 4.25 (s, 3H);[chiral column DaicelChiralpakID-3 (0.46cmx15cm), normal hexane/isopropanol=70/30, v=0.7mL min-1, detection wavelength=254nm, t (minor)=8.59min, t (major)=11.46min], 95:5er; [α]D 27=+414.1 (c=1.00, chloroforms).
O-15:
73% yield (yield).1HNMR(400MHz,CDCl3) δ 8.79 (d, J=5.2Hz, 1H), 8.27 (d, J=7.6Hz, 1H), 7.96 (d, J=8.8Hz, 1H), 7.86-7.76 (m, 3H), 7.47 (d, J=8.4Hz, 1H), 7.42-7.37 (m, 2H), 7.34-7.24 (m, 4H), 7.17-7.13 (m, 1H), 7.03-6.92 (m, 4H), 6.81 (s, 1H), 6.13 (d, J=15.6Hz, 1H), 3.98 (s, 3H), 3.21 (s, 3H); [chiral column DaicelChiralpakID-3 (0.46cmx15cm), normal hexane/isopropanol=50/50, v=0.7mL min-1, detection wavelength=254nm, t (major)=13.61min, t (minor)=21.42min], 97:3er; [α]D 28=+207.1 (c=1.00, chloroforms).
O-16:
56% yield (yield).1HNMR(400MHz,CDCl3) δ 8.84 (d, J=5.2Hz, 1H), 8.34 (d, J=8.4Hz, 1H), 7.94 (d, J=8.8Hz, 1H), 7.86-7.73 (m, 3H), 7.54 (d, J=8.8Hz, 1H), 7.45-7.37 (m, 2H), 7.22-7.13 (m, 3H), 7.05-7.01 (m, 2H), 6.58 (d, J=15.6Hz, 1H), 4.16 (s, 3H), 2.82 (s, 3H), 2.80 (s, 3H); [chiral column DaicelChiralpakID-3 (0.46cmx15cm), normal hexane/isopropanol=50/50, v=0.7mL min-1, detection wavelength=254nm, t (major)=20.52min, t (minor)=33.07min], 98:2er; [α]D 28=+273.5 (c=1.00, chloroforms).
O-17:
84% yield (yield).1HNMR(400MHz,CDCl3) δ 8.86 (d, J=5.2Hz, 1H), 8.37 (d, J=8.0Hz, 1H), 7.96 (d, J=8.8Hz, 1H), 7.86-7.80 (m, 3H), 7.52-7.37 (m, 3H), 7.29-7.22 (m, 1H), 7.19-7.11 (m, 2H), 7.07-7.02 (m, 1H), 6.90 (dd, J=22.4,17.6Hz, 1H), 6.17-6.04 (m, 1H), 4.16 (s, 3H), 3.76-3.47 (m, 4H), 1.04 (t, J=7.2Hz, 3H), 0.95 (t, J=7.2Hz, 3H); [chiral column DaicelChiralpakID-3 (0.46cmx15cm), normal hexane/isopropanol=50/50, v=0.7mL min-1, detection wavelength=254nm, t (major)=7.56min, t (minor)=11.83min], 93:7er; [α]D 27=+219.1 (c=1.00, chloroforms).
O-18:
37% yield (yield).1HNMR(400MHz,CDCl3) δ 8.87 (d, J=5.2Hz, 1H), 8.33 (d, J=8.4Hz, 1H), 7.96 (d, J=8.4Hz, 1H), 7.83-7.80 (m, 3H), 7.62 (d, J=8.8Hz, 1H), 7.43-7.38 (m, 2H), 7.23-7.14 (m, 2H), 7.11-6.95 (m, 2H), 6.26 (dd, J=17.2,10.8Hz, 1H), 5.69 (d, J=17.2Hz, 1H), 5.00 (d, J=10.8Hz, 1H), 4.16 (s, 3H); [chiral column DaicelChiralpakIC (0.46cmx25cm), normal hexane/isopropanol=60/40, v=0.7mL min-1, detection wavelength=254nm, t (major)=11.40min, t (minor)=20.44min], 96:4er; [α]D 29=+199.0 (c=0.20, chloroforms).
Application Example 3:
General reactions operation: under nitrogen protection, K (10 μm of ol) and benzoyl peroxide (BzO)2(2.4mg, 10 μm of ol) are dissolved in methanol (0.5mL), react 30min under room temperature. Sequentially add biaryl substrate (0.2mmol), 2-vinyl naphthalene (0.24mmol), Schweinfurt green (7.3mg, 0.04mmol), Ag2CO3(55.2mg, 0.2mmol), methanol (0.5mL), reacts at 25 DEG C.TLC follows the tracks of after reacting completely, and uses saturated sodium bicarbonate solution cancellation, dichloromethane extraction, and anhydrous sodium sulfate dries, and filters removal of solvent under reduced pressure, and column chromatography purifies (petroleum ether/acetone=30/1). The ee value of product is measured by HPLC.

Claims (13)

1. cyclopentadiene rhodium complex (S)-K or (R)-K based on 1, a 1'-spirobindene alkane skeleton, it is structured with the optical pure compound of formula:
Wherein, R1Selected from H, C1～C16 alkyl, C1～C16 perfluoroalkyl, C1～C16 alkoxyl or benzyloxy.
2. as claimed in claim 11, cyclopentadiene rhodium complex (the S)-K or (R)-K of 1'-spirobindene alkane skeleton, it is characterized in that, cyclopentadiene rhodium complex (the S)-K or (R)-K of 1,1'-described spirobindene alkane skeleton is arbitrary compound as described below:
3. cyclopentadiene (the S)-I of a spirobindene alkane skeleton, (R)-I, (S)-I ' or (R)-I ' compound, is characterized in that being structured with the compound of formula:
Wherein, R1With described in claim 1.
4. one kind as claimed in claim 11, the synthetic method of cyclopentadiene rhodium complex (the S)-K or (R)-K of 1'-spirobindene alkane skeleton, it is characterized in that in organic solvent, 25 DEG C to 80 DEG C, there is cyclopentadiene (S)-I and (S)-I ' or (R)-I and (R)-I ', ethanol thallium and the [Rh (C of 1,1'-spirobindene alkane skeleton2H4)2Cl]2React 8 hours to 24 hours;
Described cyclopentadiene (the S)-I and (S)-I ' with 1,1'-spirobindene alkane skeleton or (R)-I and (R)-I ', ethanol thallium, [Rh (C2H4)2Cl]2Mol ratio be 1:1:(1～1.2): (0.5～0.6);
Described organic solvent is polarity or non-polar solven;
Cyclopentadiene (the S)-I of described 1,1'-spirobindene alkane skeleton, (R)-I, (S)-I ' or (R)-I ' compound are as claimed in claim 3.
5. have 1 as claimed in claim 3, cyclopentadiene (the S)-I of 1'-spirobindene alkane skeleton, (R)-I, (S)-I ' or (R)-I ' compound, it is characterized in that, described has cyclopentadiene (the S)-I of 1,1'-spirobindene alkane skeleton, (R)-I, (S)-I ' or (R)-I ' for arbitrary compound as described below:
6. one kind as claimed in claim 3 based on 1, the synthetic method of cyclopentadiene (the S)-I of 1'-spirobindene alkane skeleton, (R)-I, (S)-I ' or (R)-I ' compound, it is characterized in that in organic solvent, 0 DEG C to 80 DEG C, (S)-II or (R)-II, sodium hydride, cyclopentadienyl sodium and the 15-crown-5 with 1,1'-spirobindene alkane skeleton react 24 hours; (the S)-II or (R)-II of the described 1,1'-of having spirobindene alkane skeleton, sodium hydride, cyclopentadienyl sodium, 15-crown-5 mol ratio be 1:(1～1.4): (1～1.4): 2; Subsequently, in organic solvent with 200-240 DEG C, carry out thermal rearrangement and react 16-36 hour;
Described organic solvent is toluene, n-dodecane;
(the S)-II or (R)-II of the described 1,1'-of having spirobindene alkane skeleton are structured with formula:
Wherein, R1With described in claim 1, X is selected from Cl, Br, I, OTs, OMs.
7. method as claimed in claim 6, it is characterized in that described having 1, (S)-II or (R)-II compound of 1'-spirobindene alkane skeleton are obtained by following method, in chloroform, 25 DEG C to 80 DEG C, have benzylalcohol (the S)-III or (R)-III of 1,1'-spirobindene alkane skeleton, thionyl chloride, pyridine react 24 hours to 48 hours; Benzylalcohol (the S)-III or (R)-III of the described 1,1'-of having spirobindene alkane skeleton, thionyl chloride, pyridine mol ratio be 1:1:(5～10);
Or in dichloromethane, 0 DEG C to 25 DEG C, there is benzylalcohol (the S)-III or (R)-III of 1,1'-spirobindene alkane skeleton, mesyl chloride (or to this sulfonic acid chloride of methyl) and triethylamine and react 24 hours to 48 hours; The mol ratio of benzylalcohol (the S)-III or (R)-III of the described 1,1'-of having spirobindene alkane skeleton, mesyl chloride (or to this sulfonic acid chloride of methyl) and triethylamine is 1:(2～6): (2～6);
Benzylalcohol (the S)-III or (R)-III of the described 1,1'-of having spirobindene alkane skeleton are structured with formula:
Wherein, R1With described in claim 1.
8. method as claimed in claim 7, it is characterized in that described having 1, benzylalcohol (S)-III or (R)-III compound of 1'-spirobindene alkane skeleton are obtained by following method, when in organic solvent with 80 DEG C, compound (S)-IV or (R)-IV, Hydro-Giene (Water Science)., 1,10-phenanthroline and cesium carbonate react 24 hours to 48 hours;
The mol ratio of described compound (S)-IV or (R)-IV, Hydro-Giene (Water Science)., 1,10-phenanthroline and cesium carbonate is 1:0.2:0.4:2;
Described organic solvent is methanol, ethanol, butanol, trifluoroethanol, 1-propenol-3, benzyl alcohol;
Described compound (S)-IV or (R)-IV is structured with formula:
9. method as claimed in claim 8, it is characterized in that described compound (S)-IV or (R)-IV compound are obtained by following method, in organic solvent, compound (S)-V or (R)-V and diisobutyl aluminium hydride react 8 hours;
The mol ratio of described compound (S)-V or (R)-V and diisobutyl aluminium hydride is 1:(4～6);
The temperature of described reaction is-78 DEG C and reacts 1～3 hour, then reacts under room temperature 1～5 hour again;
Described compound (S)-V or (R)-V is structured with formula:
10. a method as claimed in claim 9, it is characterized in that described compound (S)-V or (R)-V compound are obtained by following method, after compound (S)-VI or (R)-VI reacts 5～8 hours with excessive thionyl chloride, boil off unnecessary thionyl chloride, add excessive methanol and obtain;
The temperature of described reaction is 80 DEG C of reactions;
Described compound (S)-VI or (R)-VI is structured with formula:
11. method as claimed in claim 10, it is characterized in that described compound (S)-VI or (R)-VI prepares by the following method: in organic solvent, with palladium compound for catalyst, under the existence of iodobenzene acetate, under the effect of iodine, compound (S)-VII or (R)-VII occurs intermolecular c h bond iodination reaction to obtain;
Described palladium compound is one or more in palladium, trifluoracetic acid palladium, Palladous chloride., two (acetylacetone,2,4-pentanedione) palladiums and allyl palladium chloride;
Described organic solvent is N-Methyl pyrrolidone, dimethyl sulfoxide, N, one or more in dinethylformamide, DMAC N,N' dimethyl acetamide, toluene, o-Dimethylbenzene, meta-xylene, xylol, hexamethylene, normal hexane, normal heptane, dioxane and acetonitrile;
Described compound (S)-VII or the mol ratio of (R)-VII, alkali, palladium compound and oxidant are 1:(2.0～8.0): (0.01～0.4): (2.0～8.0);
The temperature of described intermolecular asymmetric c h bond arylation reaction is 80～120 DEG C, it is advantageous to be 100～120 DEG C.
12. cyclopentadiene rhodium complex (S)-K or (the R)-K application in asymmetric oxidation Heck coupled catalytic reaction of 1,1'-spirobindene alkane skeleton as claimed in claim 1.
13. as claimed in claim 12 1; cyclopentadiene rhodium complex (S)-K or (the R)-K application in asymmetric oxidation Heck coupled catalytic reaction of 1'-spirobindene alkane skeleton; it is characterized in that; described application comprises the steps: under inert gas shielding; in organic solvent; under the effect of benzoyl peroxide and compound (S)-K or (R)-K; under oxidant participates in; aryl-linking compound M and alkene N is carried out asymmetric oxidation Heck coupling reaction
Described organic solvent is methanol;
Described oxidant is Disilver carbonate and Schweinfurt green;
Described aryl-linking compound M, alkene N, compound (S)-K, benzoyl peroxide, the mol ratio of Schweinfurt green and silver oxide is 1:(1.0～2.0): (0.05～0.1): (0.05～0.1): (0.02～1.0): (1.0～2.0), it is advantageous to for 1:1.2:0.05:0.05:0.2:1.0;
The temperature of described asymmetric oxidation Heck coupling reaction is 25～80 DEG C.
CN201610120414.7A 2016-03-03 2016-03-03 Cyclopentadiene compound based on spiro-skeleton and rhodium complex thereof, synthesis method and application Active CN105669766B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201610120414.7A CN105669766B (en) 2016-03-03 2016-03-03 Cyclopentadiene compound based on spiro-skeleton and rhodium complex thereof, synthesis method and application

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201610120414.7A CN105669766B (en) 2016-03-03 2016-03-03 Cyclopentadiene compound based on spiro-skeleton and rhodium complex thereof, synthesis method and application

Publications (2)

Publication Number Publication Date
CN105669766A true CN105669766A (en) 2016-06-15
CN105669766B CN105669766B (en) 2020-03-10

Family

ID=56306655

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201610120414.7A Active CN105669766B (en) 2016-03-03 2016-03-03 Cyclopentadiene compound based on spiro-skeleton and rhodium complex thereof, synthesis method and application

Country Status (1)

Country Link
CN (1) CN105669766B (en)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109180579A (en) * 2018-10-29 2019-01-11 四川大学 A kind of high-efficient synthesis method of 4- iodine isoquinolines
CN109354579A (en) * 2018-11-23 2019-02-19 西北大学 A kind of biaryl axial chirality benzindole-naphthalene compounds and its synthetic method
CN112592340A (en) * 2020-12-23 2021-04-02 中国科学院上海有机化学研究所 Chiral azaspiroalkene salt compound and preparation method thereof
CN114262295A (en) * 2021-12-21 2022-04-01 天津大学 Chiral quaternary ammonium salt with spiro indane skeleton and its prepn and application
CN114957103A (en) * 2022-06-29 2022-08-30 中国科学院上海有机化学研究所 Axial chiral halogenated biaryl compound and preparation method thereof
CN115093313A (en) * 2022-08-02 2022-09-23 中国科学院上海有机化学研究所 Cyclopentadiene derived from multi-methyl substituted spiroindane, rhodium complex thereof, preparation method, intermediate and application

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6242941A (en) * 1985-08-19 1987-02-24 Mitsui Toatsu Chem Inc Production of 6,6'-dihydroxy-3,3,3',3'-tetramethyl-1,1'-spirobiindane

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6242941A (en) * 1985-08-19 1987-02-24 Mitsui Toatsu Chem Inc Production of 6,6'-dihydroxy-3,3,3',3'-tetramethyl-1,1'-spirobiindane

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
BAIHUA YE等: "Chiral Cyclopentadienyls: Enabling Ligands for Asymmetric Rh(III)-Catalyzed C-H Functionalizations", 《ACC. CHEM. RES.》 *
JUN ZHENG 等: "Asymetric Dearomatization of Naphthols via a Rh-Catalyzed C(sp2)-H Funcionalization/Annulation Reaction", 《J.AM.CHEM.SOC.》 *
ZHENG, JUN 等: "Construction of Axial Chirality by Rhodium-Catalyzed Asymmetric Dehydrogenative Heck Coupling of Biaryl Compounds with Alkenes", 《ANGEW. CHEM.》 *
刘全忠: "1,1"-螺二茚烷-7,7"-二羧酸的制备", 《西华师范大学学报（自然科学版）》 *

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109180579A (en) * 2018-10-29 2019-01-11 四川大学 A kind of high-efficient synthesis method of 4- iodine isoquinolines
CN109354579A (en) * 2018-11-23 2019-02-19 西北大学 A kind of biaryl axial chirality benzindole-naphthalene compounds and its synthetic method
CN112592340A (en) * 2020-12-23 2021-04-02 中国科学院上海有机化学研究所 Chiral azaspiroalkene salt compound and preparation method thereof
CN112592340B (en) * 2020-12-23 2023-01-17 中国科学院上海有机化学研究所 Chiral azaspiroalkene salt compound and preparation method thereof
CN114262295A (en) * 2021-12-21 2022-04-01 天津大学 Chiral quaternary ammonium salt with spiro indane skeleton and its prepn and application
CN114957103A (en) * 2022-06-29 2022-08-30 中国科学院上海有机化学研究所 Axial chiral halogenated biaryl compound and preparation method thereof
CN114957103B (en) * 2022-06-29 2024-06-28 中国科学院上海有机化学研究所 Axial chiral halogenated biaryl compound and preparation method thereof
CN115093313A (en) * 2022-08-02 2022-09-23 中国科学院上海有机化学研究所 Cyclopentadiene derived from multi-methyl substituted spiroindane, rhodium complex thereof, preparation method, intermediate and application
CN115093313B (en) * 2022-08-02 2023-08-11 中国科学院上海有机化学研究所 Multi-methyl substituted spiroindane derivative cyclopentadiene, rhodium complex, preparation method, intermediate and application thereof

Also Published As

Publication number Publication date
CN105669766B (en) 2020-03-10

Similar Documents

Publication Publication Date Title
CN105669766A (en) Spiro-framework-based cyclopentadiene compounds, rhodium complexes, and synthesis method and application thereof
Fu et al. First examples of a tosylate in the palladium-catalyzed Heck cross coupling reaction
CN113214129B (en) Method for iodination/sulfonylation reaction of 1, 6-diene compound initiated by sulfonyl free radical
CN113429330A (en) Method for preparing 2-pyrrolidone derivative through three-component serial cyclization reaction under catalysis of copper
CN110551115B (en) Oxazoline ligand, preparation method and application thereof
CN110590639B (en) Preparation method of 3-nitro-2-indolone compound
CN114956924A (en) Method for synthesizing polyfluoro biaryl through series/coupling reaction
CN111233617A (en) Synthesis method of 1-iodoalkyne compound
KR100220645B1 (en) Process for producing benzene derivatives
CN111718372B (en) Axial chiral phosphine-alkene ligand and preparation method and application thereof
CN113666826A (en) Method for methoxylation of aryl or heteroaryl
US9670240B2 (en) Cyclic phosphinate derivatives and method of preparing the same
CN115109060A (en) Method for selectively synthesizing quinoline-2-ketone by copper-catalyzed alpha-bromocarbonyl alkyne and maleimide serial cyclization
Wu et al. Heterogeneous chitosan@ nickel (II)-catalyzed tandem radical cyclization of N-arylacrylamides: A general method for constructing fluorinated 3, 3-disubstituted oxindoles using perfluoroalkyl iodides
CN104558014B (en) Chiral N-heterocyclic carbene precursor salt with 3,4-dihydroisoquinoline skeleton, synthetic method and application
CN114957103A (en) Axial chiral halogenated biaryl compound and preparation method thereof
CN109232282B (en) Synthetic method of 2-aminobenzophenone compound
CN109678911B (en) Ferrocene compound and preparation method thereof
CN110563659B (en) Method for preparing 1,2, 3-triazole compound by heterogeneous copper catalysis in one pot
JPH11343287A (en) Production of isochroman-3-one
CN107382642B (en) α -diphenyl-1-aryl propenone compound preparation method
US4216153A (en) Method of preparing phthalide
CN109796391B (en) Preparation method of thiosulfonate compound in water phase
CN110105259B (en) Method for removing sulfinyl in heteroarene compound
CN113403635B (en) Method for preparing N-substituted pyrrolidone derivative

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant