CN104327121A - Spiro monodentate complex, and preparation method and application thereof - Google Patents

Spiro monodentate complex, and preparation method and application thereof Download PDF

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Publication number
CN104327121A
CN104327121A CN201410662121.2A CN201410662121A CN104327121A CN 104327121 A CN104327121 A CN 104327121A CN 201410662121 A CN201410662121 A CN 201410662121A CN 104327121 A CN104327121 A CN 104327121A
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spiro
reaction
compound
preparation
application
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CN104327121B (en
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王巧峰
张生勇
秦向阳
王平安
李晓晔
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Fourth Military Medical University FMMU
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    • 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 System
    • C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic System compounds of the platinum group
    • C07F15/0046—Ruthenium 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
    • B01J31/22—Organic complexes
    • B01J31/2282—Unsaturated compounds used as ligands
    • B01J31/2291—Olefins
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D309/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings
    • C07D309/02—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings having no double bonds between ring members or between ring members and non-ring members
    • C07D309/08—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings having no double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D309/10—Oxygen atoms
    • 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
    • C07F11/00—Compounds containing elements of Groups 6 or 16 of the Periodic System
    • 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
    • B01J2231/48—Ring-opening reactions
    • B01J2231/482—Ring-opening reactions asymmetric reactions, e.g. kinetic resolution of racemates
    • 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
    • B01J2531/60—Complexes comprising metals of Group VI (VIA or VIB) as the central metal
    • B01J2531/64—Molybdenum
    • 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
    • B01J2531/60—Complexes comprising metals of Group VI (VIA or VIB) as the central metal
    • B01J2531/66—Tungsten
    • 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
    • B01J2531/821—Ruthenium

Abstract

The invention discloses a spiro monodentate complex disclosed as structural general formula (I), wherein R is halogen, nitro group, C1-C4 alkyl group or C1-C4 alkoxy group, R1 is 2,6-diisopropylphenyl or adamantyl group, and M is Ru, Mo or W. The compound can catalyze asymmetric ring opening/cross double-decomposition reaction of olefins.

Description

A kind of volution monodentate title complex and preparation method thereof and application
Technical field
The present invention relates to the title complex and preparation method thereof of a class based on " stereogenic-at-metal " of spirane structure.
Background technology
Olefin metathesis reaction forms one of strong method of C=C key, and this reaction not only can prepare complicated alkene by simple olefins; And produce by product in reaction hardly or only produce this by product very easily removed of ethene.Since last century, this reaction was found, its research and development is gained great popularity, be widely used in the synthesis of macromolecular material and organic intermediate.Due to the singularity of this reaction, the catalyzer of " universality " can not be there is, thus need people constantly to inquire into the catalyzer being applicable to various different substrates.Understand according to contriver, " stereogenic-at-metal " unidentate ligand chiral catalyst structure had been reported is only limitted to BINOL type or biphenyl type unidentate ligand catalyzer.
Summary of the invention
An object of the present invention is to provide a kind of volution monodentate stereogenic-at-metal title complex;
Another object of the present invention is to provide the preparation method of above-mentioned title complex;
A further object of the invention is to provide the application of above-mentioned composition catalyst in asymmetric replacement(metathesis)reaction.
Implementation procedure of the present invention is as follows:
Compound shown in structural formula (I),
Wherein, R is halogen, nitro, the alkyl of a 1-4 carbon atom, the alkoxyl group of a 1-4 carbon atom;
R 12,6-diisopropyl phenyl or adamantyl;
M is Ru, Mo or W.
In above-claimed cpd, spiro indan skeleton can be raceme or single rotator.
The preparation method of structural formula (I) compound is as follows,
Under-50 degree, be added drop-wise in compd A diethyl ether solution by the diethyl ether solution of compd B, be slowly warming up to room temperature, reaction color fades to redness, removal of solvent under reduced pressure, obtains Compound C with Skellysolve A recrystallization.
Above-claimed cpd can be applicable in the asymmetric replacement(metathesis)reaction of alkene.
Advantage of the present invention and positively effect: in structure of the present invention, spiro indan structure is the outstanding chiral induction source of a class, it, as part next-door neighbour metal chiral center, produces good chiral induction effect to replacement(metathesis)reaction.
Embodiment
The present invention will be further described by the following examples.
Embodiment 1 ( s) synthesis of-6,6'-bis-bromo-spiro indan diphenol
Under nitrogen protection, by 0.252g (1mmol) volution diphenol and DIPA (0.1mL, 0.5mmol) be placed in 5 mL methylene dichloride, lower stirring at 0 DEG C, be that 0.1mol/L NBS/ dichloromethane solution is slowly added drop-wise in this system again by 10mL concentration, Keep agitation 6 hours; TLC detection reaction stops, and uses CH 2cl 2extraction, organic over anhydrous dried over mgso, sherwood oil: under ethyl acetate (V/V)=7:1 condition, column chromatography for separation obtains product, fusing point 152-154 DEG C of sign conforms to structure.H NMR（300，） δ 7.31（d，2H），6.74（d，2H），5.25（s，2H），2.95-3.06（m，4H），2.36-2.41（m，2H），2.21-2.27（m，2H）。
The synthesis of embodiment 2 chirality spiro indan derivative
Under nitrogen atmosphere, will ( s)-6,6'-bis-bromo-spiro indan diphenol (0.1g, 0.19mmol) are dissolved in 10mL methylene dichloride, add 0.1mL triethylamine, stir at 22 DEG C; Add 0.2 mL TBSOTf fast, continue to stir 10min, terminate by TLC detection reaction, use CH 2cl 2extraction, organic over anhydrous dried over mgso, rotary evaporation except desolventizing, with sherwood oil: ethyl acetate (v:v=10:1) column chromatography obtains sterling, fusing point 144-146 DEG C. 1HNMR（400Hz，DCl 3） δ7.37（d，2H）6.68-6.77（d，2H），5.20（m，1H)，2.87-2.97（m，4H），2.23-2.26（m，2H），2.11-2.14（m，2H），0.81（s，9H），0.15（m，6H）。
Embodiment 3
With R=Br, R 1=2,6- i-Pr 2c 6h 3for example, in glove box, under-50 degree, 150 mg A and 4 mL ether are placed in sealed vessel stir, also seal filling the Nike of executing that 0.6 mL contains the diethyl ether solution of 133 mg B at glove box simultaneously, be cooled to-50 degree, now B dropper is joined in solution A, and with 0.6 mL ether, B is moved in A container completely again, the system of mixed solution continues to stir, slowly be warming up to room temperature, reaction color fades to redness, after 2 hours, system removal of solvent under reduced pressure, the resistates obtained 5 mL Skellysolve As dissolve, decompression removing Skellysolve A, obtain powdery product, again this powdery solid to be dissolved in 2 mL Skellysolve As and to stir, after all solids dissolves, system is closed, be placed in-50 and spend night, a large amount of needle-like red crystals is had to separate out, collect and obtain product C.
The chiral spiro monodentate part synthesis result of embodiment 4 containing different substituents
The application of embodiment 5 chiral spiro monodentate part in asymmetric open loop/cross-metathesis
Under room temperature, in glove box, by commercially available reagent A(10 mg, 16.9 μmol) and above-mentioned chirality spiro indan derivative B(8.82 mg, 16.9 μand benzene (845 mol) μl, 0.02M) be placed in single port bottle stirring 2 hours, solution colour fades to orange, obtains product C; Add vinylbenzene (0.42mL, 3.5mmol) Keep agitation again after 5 minutes, add bridged ring substrate D(0.42g, 1.8mmol) 8mL benzole soln, keep its concentration to be 0.2M, Keep agitation 1 hour, stopped reaction, reaction system is taken out from glove box.Concentrated removal solvent, product obtains light yellow product through column chromatography, productive rate 65%. 1HNMR（400Hz，DCl 3） δ7.33-7.6（m，5H）,6.61（d，1H），5.80（d，1H)，5.25-5.7（m，3H），4.25-4,28（m，2H），3.21（s，3H），2.8（t，1H），1.5-1.7（m，4H）。

Claims (4)

1. the compound shown in general structure (I),
Wherein, R is halogen, nitro, the alkyl of a 1-4 carbon atom, the alkoxyl group of a 1-4 carbon atom;
R 12,6-diisopropyl phenyl or adamantyl;
M is Ru, Mo or W.
2. compound according to claim 1, is characterized in that: spiro indan skeleton is raceme or single rotator.
3. the preparation method of compound described in claim 1, is characterized in that:
Under-50 degree, be added drop-wise in compd A diethyl ether solution by the diethyl ether solution of compd B, be slowly warming up to room temperature, reaction color fades to redness, removal of solvent under reduced pressure, obtains Compound C with Skellysolve A recrystallization.
4. the application of compound described in claim 1 in the asymmetric replacement(metathesis)reaction of alkene.
CN201410662121.2A 2014-11-19 2014-11-19 A kind of loop coil monodentate complex and preparation method and application Expired - Fee Related CN104327121B (en)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1827563A (en) * 2006-04-06 2006-09-06 武汉大学 Process for preparing 1,1'-spiro indan or derivatives thereof
EP2703081A1 (en) * 2012-09-04 2014-03-05 XiMo AG Molybdenum and tungsten complexes as olefin metathesis catalysts and reactions using the catalysts
CN103797009A (en) * 2011-06-03 2014-05-14 麻省理工学院 Z-selective ring-closing metathesis reactions
CN104039801A (en) * 2011-11-07 2014-09-10 麻省理工学院 Tungsten oxo alkylidene complexes for Z selective olefin metathesis

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1827563A (en) * 2006-04-06 2006-09-06 武汉大学 Process for preparing 1,1'-spiro indan or derivatives thereof
CN103797009A (en) * 2011-06-03 2014-05-14 麻省理工学院 Z-selective ring-closing metathesis reactions
CN104039801A (en) * 2011-11-07 2014-09-10 麻省理工学院 Tungsten oxo alkylidene complexes for Z selective olefin metathesis
EP2703081A1 (en) * 2012-09-04 2014-03-05 XiMo AG Molybdenum and tungsten complexes as olefin metathesis catalysts and reactions using the catalysts

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
MARGARET M. FLOOK等，: "Z-Selective Olefin Metathesis Processes Catalyzed by a Molybdenum Hexaisopropylterphenoxide Monopyrrolide Complex", 《J. AM. CHEM. SOC.》 *

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