CN102584736B - Method for catalyzing and oxidizing hydroxamic acids - Google Patents
Method for catalyzing and oxidizing hydroxamic acids Download PDFInfo
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- CN102584736B CN102584736B CN2012100124503A CN201210012450A CN102584736B CN 102584736 B CN102584736 B CN 102584736B CN 2012100124503 A CN2012100124503 A CN 2012100124503A CN 201210012450 A CN201210012450 A CN 201210012450A CN 102584736 B CN102584736 B CN 102584736B
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- azanol
- ambient temperature
- tertbutyloxycarbonyl
- rhodium
- reaction
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- 0 *N1OC2C=CC1C2 Chemical compound *N1OC2C=CC1C2 0.000 description 1
- KQXGPTFHMCENRO-RBUKOAKNSA-N CC(C)(C)OC(N([C@@H](C=C1)c2ccccc2)O[C@H]1c1ccccc1)=O Chemical compound CC(C)(C)OC(N([C@@H](C=C1)c2ccccc2)O[C@H]1c1ccccc1)=O KQXGPTFHMCENRO-RBUKOAKNSA-N 0.000 description 1
Abstract
The invention discloses a method for catalyzing and oxidizing hydroxamic acids. In the method, at a room temperature, a caprolactam rhodium and tert-butyl hydroperoxide catalytic-oxidation system is used, and oxidation is performed on hydroxylamine, acylnitroso compounds generated in situ and conjugated diene are in Die1s-Alder reaction, so that [4+2] cycloaddition products are obtained. Compared with the prior art, the method provided by the invention has the advantages of low catalyst use level, mild reaction conditions, wide substrate applicability and the like. Higher reaction yield can be obtained under relatively mild conditions.
Description
Technical field
The present invention relates to a kind of method of catalyzed oxidation acyl group azanol, use the Diels-A1der reaction to be caught it, produce the cycloaddition product of [4+2], belong to the organo-metallic catalytic field.
Background technology
Acyl group nitroso compound (acylnitroso compounds, as shown in structural formula 1) is that nitroso compound is when a class higher as the dienophile activity.Since 1940, be widely used in [4+2] cycloaddition reaction of conjugated diolefine.The assorted Diels-Alder reaction of this class is the important method (J.Org.Chem., 28,3034,1963) of the natural product such as synthesis of polyhydroxy alkaloid, oxazine derivatives.
Acylnitroso?compounds
The acyl group nitroso compound
The acyl group nitroso compound is mainly prepared by the in-situ oxidation by the acyl group azanol, due to acyl group nitroso compound unstable (being easy to dimerization), therefore by the conjugated diolefine Diels-Alder that mixes with it, reacts to catch.The method of oxidation azanol is many especially, mainly comprises periodate oxidation (Synth.Commun., 30,947,2000), plumbic oxide oxidation (Can.J.Chem., 57,1712,1979).Hypochlorite oxidation (J.Org.Chem., 64,4976,1999), Swern oxidation (Tetrahedron Letter., 33,3583,1992) etc.But above-mentioned these oxygenant toxicity are large, reaction conditions is comparatively harsh, side reaction is many.Within 2002, the people such as Whiting have reported a kind of use ruthenium (Ru) title complex, and at ambient temperature, the catalyzed oxidation azanol prepares the method (J.Chem.Soc.Perkin Tran s.1,2058,2002) of acyl group nitroso compound.Although this method reaction conditions gentleness, the catalyzer preparation is not easy relatively, productive rate is not high yet.It is at ambient temperature a kind of that the people such as Whiting in 2011 have further reported, air, as oxygenant, is used CuCl
2The catalyzed oxidation azanol prepares the method (Org.Lett., 13,3442,2011) of acyl group nitroso compound, and the method has nontoxicity, reaction conditions gentleness, productive rate advantages of higher, but needs extra part and the higher catalyst levels of using.
Hexanolactam rhodium [Rh
2(cap)
4] be a kind of acid amides rhodium class title complex (J.Am.Chem.Soc., 115,958,1993) of the preparation such as Doyle in 1993.Hexanolactam rhodium [Rh
2(cap)
4] to benzyl position oxidizing reaction (Org.Lett.; 7; 5167; 2005), allylic oxidation reaction (J.Am.Chem.Soc.; 126; 13622; 2004 and U.S.'s patent of invention publication number: US 2009/0093638), amine oxidation-Mannich addition successive reaction (J.Am.Chem.Soc.; 128; 5648; 2006) etc. there is higher reactive behavior and selectivity, but the reaction (simultaneously using the conjugated diolefine original position to catch this acyl group nitroso compound) of using this catalyst oxidation acyl group azanol to prepare the acyl group nitroso compound there is no report.
Rh
2(cap)
4
The hexanolactam rhodium
The invention provides a kind of use hexanolactam rhodium [Rh
2(cap)
4] title complex, catalyzed oxidation acyl group azanol prepares the acyl group nitroso compound, uses the conjugated diolefine original position to catch the method for this acyl group nitroso compound simultaneously, and the method is simple to operate, reaction conditions is gentle, high yield.
Summary of the invention
The object of the present invention is to provide a kind of method of catalyzed oxidation acyl group azanol; the method at ambient temperature; use divalence rhodium complex---hexanolactam rhodium (as shown in structural formula 2); catalysis-oxidation system with peroxy tert-butyl alcohol; azanol is carried out to oxidation; generated in-situ acyl group nitroso compound reacts by with conjugated diolefine, Diels-Alder occurring, and obtains the cycloaddition product of [4+2].The method can obtain higher reaction yield under relatively gentle condition.
The method of a kind of catalyzed oxidation acyl group azanol of the present invention, and use conjugated diolefine to catch oxidation products acyl group nitroso compound original position, the method follows these steps to carry out:
A, the tertbutyloxycarbonyl azanol is dissolved in methylene dichloride, adds the dichloromethane solution of hexanolactam rhodium, stir at ambient temperature;
B, add conjugated diolefine again, after stirring at ambient temperature 10 minutes, slowly drip the n-decane solution of peroxy tert-butyl alcohol, till being stirred at ambient temperature reaction and finishing, obtain crude product;
C, by crude product decompressing and extracting solvent, use sherwood oil: ethyl acetate=carry out column chromatography for separation at 10: 1 can obtain target product.
In step a, the mol ratio of tertbutyloxycarbonyl azanol and hexanolactam rhodium is 1: 0.001-0.01.
In step a, the tertbutyloxycarbonyl azanol is 1 in the mol ratio of peroxy tert-butyl alcohol: 2-4.
In step b, conjugated diolefine is cyclohexadiene, cyclopentadiene, cycloheptadiene, 1,3-pentadiene or Isosorbide-5-Nitrae-phenylbenzene-1,3 divinyl.
The mol ratio of step b tertbutyloxycarbonyl azanol and conjugated diolefine is 1: 1-1.2.
The method of a kind of catalyzed oxidation acyl group azanol of the present invention, then catch oxidation products acyl group nitroso compound original position with conjugated diolefine, and the reaction formula in the method is:
In formula: Rh
2(cap)
4For the hexanolactam rhodium, TBHP is peroxy tert-butyl alcohol, and DCM is methylene dichloride, and R is the tertiary butyl or benzyl, and rt is room temperature.
A kind of use metal catalyst hexanolactam rhodium of the present invention, the method that the in-situ oxidation of acyl group azanol prepares the acyl group nitroso compound and with the Diels-Alder reaction, it caught follows these steps to carry out:
Add azanol (1 equivalent) and metal catalyst hexanolactam rhodium (0.1mo%) in reaction flask, take methylene dichloride as solvent, under stirring at room, add corresponding conjugated diolefine (1.2 equivalent), reaction was stirred after 10 minutes, then added superoxide (4 equivalent), after thin-layer chromatography (TLC) detection reaction finishes, the decompressing and extracting solvent, carry out column chromatography for separation, obtains target product.
Compared with prior art, the present invention has that post-reaction treatment is simple to operate, productive rate is high, easily prepared by catalyzer, the advantages such as consumption is few, substrate wide adaptability.
Embodiment
In order further to set forth the present invention, below provide the concrete steps of several embodiment:
Embodiment 1:
(66.6mg, 0.5mmol) tertbutyloxycarbonyl azanol is dissolved in the 2.5mL methylene dichloride, adds and contain (0.37mg, 0.1mol%) hexanolactam rhodium [Rh
2(cap)
4] (catalyst dissolution wiring solution-forming in methylene dichloride is used), stir at ambient temperature;
Then add (48mg, 0.6mmol) cyclohexadiene, after stirring at ambient temperature 10 minutes, more slowly drip the n-decane solution (5.5M) of 2mmol peroxy tert-butyl alcohol, till being stirred at ambient temperature reaction and finishing, obtain crude product;
Reaction by crude product decompressing and extracting solvent, is used sherwood oil after finishing: ethyl acetate=carry out column chromatography for separation at 10: 1, obtain target product 97.3mg, and colorless oil, productive rate is 92%.
1H?NMR(400MHz，CDCl
3)δ1.30-1.52(m，2H)，1.47(s，9H)，2.06-2.18(m，2H)，4.73(m，2H)，6.50-6.57(m，2H)。
Embodiment 2:
(66.6mg, 0.5mmol) tertbutyloxycarbonyl azanol is dissolved in the 2.5mL methylene dichloride, adds and contain (0.37mg, 0.1mol%) hexanolactam rhodium [Rh
2(cap)
4] dichloromethane solution, stir at ambient temperature;
Then add (40mg, 0.6mmol) cyclopentadiene, after stirring at ambient temperature 10 minutes, more slowly drip the n-decane solution (5.5M) of 2mmol peroxy tert-butyl alcohol, till being stirred at ambient temperature reaction and finishing, obtain crude product;
Reaction by crude product decompressing and extracting solvent, is used sherwood oil after finishing: ethyl acetate=carry out column chromatography for separation at 10: 1, obtain target product 91mg, and colorless oil, productive rate is 92%.
1H?NMR(400MHz，CDCl
3)δ1.47(s，9H)，1.73(d，J＝8.4Hz，1H)，1.98(dt，J＝8.4Hz，J＝2.0Hz，2H)，4.98(m，2H)，5.20(m，2H)，6.40(m，2H)。
Embodiment 3:
(66.6mg, 0.5mmol) tertbutyloxycarbonyl azanol is dissolved in the 2.5mL methylene dichloride, adds and contain (0.37mg, 0.1mol%) hexanolactam rhodium [Rh
2(cap)
4] dichloromethane solution, stir at ambient temperature;
Then add (41mg, 0.6mmol) 1,3-pentadiene, after stirring at ambient temperature 10 minutes, more slowly drip the n-decane solution (5.5M) of 2mmol peroxy tert-butyl alcohol, till being stirred at ambient temperature reaction and finishing, obtain crude product;
Reaction by crude product decompressing and extracting solvent, is used sherwood oil after finishing: ethyl acetate=carry out column chromatography for separation at 10: 1, obtain target product 80mg, and colorless oil, productive rate is 81%.
1H?NMR(400MHz，CDCl
3)δ1.27(d，J＝6.8Hz，3H)，1.30(d，J＝6.8Hz，3H)，1.49(m，18H)，3.91-3.96(m，1H)，4.12-4.21(m，2H)，4.41-4.44(m，1H)，4.55-4.60(m，2H)，5.75-5.80(m，4H)。
Embodiment 4:
(66.6mg, 0.5mmol) tertbutyloxycarbonyl azanol is dissolved in the 2.5mL methylene dichloride, to this solution, adds and contain (0.37mg, 0.1mol%) hexanolactam rhodium [Rh
2(cap)
4] dichloromethane solution, stir at ambient temperature;
Then add (56.4mg, 0.6mmol) cycloheptadiene, after stirring at ambient temperature 10 minutes, more slowly drip the n-decane solution (5.5M) of 2mmol peroxy tert-butyl alcohol, till being stirred at ambient temperature reaction and finishing, obtain crude product;
Reaction by crude product decompressing and extracting solvent, is used sherwood oil after finishing: ethyl acetate=carry out column chromatography for separation at 10: 1, obtain target product 108mg, and white solid, productive rate is 96%.
1H?NMR(400MHz，CDCl
3)δ1.46(m，9H)，1.23-1.58(m，2H)，1.68-2.04(m，4H)，4.76(m，2H)，6.13(ddd，J＝9.2Hz，J＝6Hz，J＝1.2Hz，1H)，6.33(ddd，J＝9.2Hz，J＝6.8Hz，J＝1.2Hz，1H)。
Embodiment 5:
(66.6mg, 0.5mmol) tertbutyloxycarbonyl azanol is dissolved in the 2.5mL methylene dichloride, to this solution, adds and contain (0.37mg, 0.1mol%) hexanolactam rhodium [Rh
2(cap)
4] dichloromethane solution, stir at ambient temperature;
Then add (123.8mg, 0.6mmol) Isosorbide-5-Nitrae-phenylbenzene-1,3 divinyl, after stirring at ambient temperature 10 minutes, more slowly drip the n-decane solution (5.5M) of 2mmol peroxy tert-butyl alcohol, till being stirred at ambient temperature the reaction end, obtain crude product;
Reaction by crude product decompressing and extracting solvent, is used sherwood oil after finishing: ethyl acetate=carry out column chromatography for separation at 10: 1, obtain target product 114mg, and colorless oil, productive rate is 68%.
1H?NMR(400MHz，CDCl
3)δ1.52(m，9H)，5.59(m，2H)，6.10-6.19(m，2H)，7.30-7.55(m，10H)。
Claims (5)
1. the method for a catalyzed oxidation acyl group azanol is characterized in that following these steps to carrying out:
A, the tertbutyloxycarbonyl azanol is dissolved in methylene dichloride, adds and contain hexanolactam rhodium Rh
2(cap)
4Dichloromethane solution, stir at ambient temperature;
B, add conjugated diolefine again, after stirring at ambient temperature 10 minutes, slowly drip the n-decane solution of peroxy tert-butyl alcohol, till being stirred at ambient temperature reaction and finishing, obtain crude product;
C, by crude product decompressing and extracting solvent, use sherwood oil: ethyl acetate=carry out column chromatography for separation at 10: 1 can obtain target product.
2. method according to claim 1, is characterized in that in step a, the mol ratio of tertbutyloxycarbonyl azanol and hexanolactam rhodium is 1: 0.001-0.01.
3. method according to claim 1, is characterized in that in step a in tertbutyloxycarbonyl azanol and step b that the mol ratio of peroxy tert-butyl alcohol is 1: 2-4.
4. method according to claim 1, is characterized in that in step b, conjugated diolefine is cyclohexadiene, cyclopentadiene, cycloheptadiene, 1,3-pentadiene or Isosorbide-5-Nitrae-phenylbenzene-1,3-butadiene.
5. method according to claim 1, is characterized in that in step a in tertbutyloxycarbonyl azanol and step b that the mol ratio of conjugated diolefine is 1: 1-1.2.
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Granted publication date: 20131204 Termination date: 20210116 |