CN109096082A - A method of synthesis alpha-iodine is for cyclopentene ketone compounds - Google Patents
A method of synthesis alpha-iodine is for cyclopentene ketone compounds Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C49/00—Ketones; Ketenes; Dimeric ketenes; Ketonic chelates
- C07C49/587—Unsaturated compounds containing a keto groups being part of a ring
- C07C49/687—Unsaturated compounds containing a keto groups being part of a ring containing halogen
- C07C49/697—Unsaturated compounds containing a keto groups being part of a ring containing halogen containing six-membered aromatic rings
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C311/00—Amides of sulfonic acids, i.e. compounds having singly-bound oxygen atoms of sulfo groups replaced by nitrogen atoms, not being part of nitro or nitroso groups
- C07C311/15—Sulfonamides having sulfur atoms of sulfonamide groups bound to carbon atoms of six-membered aromatic rings
- C07C311/21—Sulfonamides having sulfur atoms of sulfonamide groups bound to carbon atoms of six-membered aromatic rings having the nitrogen atom of at least one of the sulfonamide groups bound to a carbon atom of a six-membered aromatic ring
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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
- C07C69/02—Esters of acyclic saturated monocarboxylic acids having the carboxyl group bound to an acyclic carbon atom or to hydrogen
- C07C69/12—Acetic acid esters
- C07C69/14—Acetic acid esters of monohydroxylic compounds
- C07C69/145—Acetic acid esters of monohydroxylic compounds of unsaturated alcohols
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- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/06—Systems containing only non-condensed rings with a five-membered ring
- C07C2601/10—Systems containing only non-condensed rings with a five-membered ring the ring being unsaturated
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- C07C2601/14—The ring being saturated
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- C07C2602/04—One of the condensed rings being a six-membered aromatic ring
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Abstract
The invention discloses a kind of synthesis alpha-iodines for the method for cyclopentene ketone compounds, it includes, it is golden (I) that eneyne ester, (acetonitrile) [(2- biphenyl) di-t-butyl phosphine] hexafluoro-antimonic acid are added in t-butyl methyl ether solution, confirms that raw material total overall reaction is complete by TLC after stirring 1 hour and adds N- N-iodosuccinimide.It is provided by the present invention a kind of alpha-iodine to be synthesized for the method for cyclopentene ketone compounds by non-annularity eneyne ester type compound.Entire reaction carries out at normal temperatures and pressures, has many advantages, such as that easy to operate, mild condition, substrate functional group good compatibility, product yield high, catalyst and product are easily separated.Alpha-iodine obtained is researched and developed for cyclopentene ketone compounds reactivity with higher, a kind of important organic intermediate is can be used as and is applied to the fields such as the synthesis of medicine, pesticide and natural products.
Description
Technical field
The invention belongs to chemosynthesis technical fields, and in particular to a method of synthesis alpha-iodine is for cyclopentenone.
Background technique
Halo carbonyl compounds are the important intermediates in the fields such as organic synthesis, biomedicine and pharmacy.Wherein most often
What is seen is α-halogenatedketone, and most of with potential bioactivity.For example, George Sakoulas etc. reports one kind newly
Type natural products Merochlorin A has the activity of external anti-multiple medicine gram-positive bacteria, and has and other antibacterial agents
With entirely different skeleton structure.The introducing of halogen atom will be for the functional molecular including natural products, drug etc.
Further chemical conversion provides some novel methods.
However known alpha-iodine is limited only to non-annularity alpha-iodine for ketone for the synthetic method substrate of ketone, and by non-annularity
Precursor compound efficiently synthesizes alpha-iodine generation cyclic annular ketenes and then has not been reported.The present invention provide a kind of mild condition, it is easy to operate, produce
Rate is higher, substrate applicability preferably synthesizes alpha-iodine for the preparation method of cyclopentenone, will be alpha-iodine for ketone and complicated natural production
The synthesis of object provides new approach.
Summary of the invention
Regarding the issue above, the present invention provides a kind ofSubstrate functional group good compatibility, product yield highConjunction
At alpha-iodine for the method for cyclopentenone.
In order to solve the above technical problems, the present invention provides the following technical scheme that alpha-iodine of the invention is for cyclopentene ketone
Compound, general structure of the alpha-iodine for cyclopentene ketone compounds:
In formula, R1、R2For group independent, and carbon number is 1~16；
R1For substituent group, including any one in phenyl, naphthalene, halogenophenyl, naphthenic base；
R2For substituent group, including methyl, chain-like alkyl, naphthenic base, carbonyl, ester group, benzenesulfonyl, phenyl, nitrogen-containing hetero
One of cyclic group or several combinations.
Synthesis alpha-iodine of the present invention includes the following steps: first to sequentially add for the method for cyclopentene ketone compounds
Methyl tertiary butyl ether(MTBE), eneyne ester, (acetonitrile) [(2- biphenyl) di-t-butyl phosphine] hexafluoro-antimonic acid are golden (I), and stirring passes through after 1 hour
TLC confirms that raw material total overall reaction is complete and adds N- N-iodosuccinimide, stirs 2 hours under normal temperature and pressure, then by reaction solution
Concentrated by rotary evaporation, and target product alpha-iodine is obtained for cyclopentenone by silica gel column chromatography.
Further, the eneyne ester includes eneyne ester type compound as shown below,
In formula, R1、R2With above-mentioned R1、R2It is corresponding consistent.
Further, concentration of the eneyne ester in methyl tertiary butyl ether(MTBE) is 0.1mol/L.
Further, the eneyne ester and (acetonitrile) [(2- biphenyl) di-t-butyl phosphine] hexafluoro-antimonic acid golden (I) rubs
You are than being 1: 0.02.
Further, the molar ratio of the eneyne ester and N- N-iodosuccinimide is 1: 2.
Further, the revolving speed of the revolving be 150~300rpm, temperature be 35~45 DEG C, vacuum degree be 0.05~
0.09Mpa, processing time are 5~15min.
Further, the silica gel column chromatography, using 200~300 mesh column chromatography silica gels, eluant, eluent is ethyl acetate
: petroleum ether=1~30: 100.
It is carried out at normal temperatures and pressures the utility model has the advantages that the present invention entirely reacts, there is easy to operate, mild condition, substrate official
The advantages that good compatibility, product yield high, easily separated catalyst and product can be rolled into a ball.Alpha-iodine obtained is researched and developed for cyclopentene ketone
Object reactivity with higher is closed, a kind of important organic intermediate is can be used as and is applied to medicine, pesticide and naturally produces
The fields such as the synthesis of object.
Detailed description of the invention
In order to illustrate the technical solution of the embodiments of the present invention more clearly, required use in being described below to embodiment
Attached drawing be briefly described, it should be apparent that, drawings in the following description are only some embodiments of the invention, for this
For the those of ordinary skill of field, without any creative labor, it can also be obtained according to these attached drawings other
Attached drawing.Wherein:
Fig. 1 is the nucleus magnetic hydrogen spectrum figure of compound 2a；
Fig. 2 is the nuclear-magnetism carbon spectrogram of compound 2a, and Fig. 1 and Fig. 2 show that compound 2a structure is correct；
Fig. 3 is the nucleus magnetic hydrogen spectrum figure of compound 2b；
Fig. 4 is the nuclear-magnetism carbon spectrogram of compound 2b, and Fig. 3 and Fig. 4 show that compound 2b structure is correct；
Fig. 5 is the nucleus magnetic hydrogen spectrum figure of compound 2c；
Fig. 6 is the nuclear-magnetism carbon spectrogram of compound 2c, and Fig. 5 and Fig. 6 show that compound 2c structure is correct；
Fig. 7 is the nucleus magnetic hydrogen spectrum figure of compound 2d；
Fig. 8 is the nuclear-magnetism carbon spectrogram of compound 2d, and Fig. 7 and Fig. 8 show that compound 2d structure is correct；
Fig. 9 is the nucleus magnetic hydrogen spectrum figure of compound 2e；
Figure 10 is the nuclear-magnetism carbon spectrogram of compound 2e, and Fig. 9 and Figure 10 show that compound 2e structure is correct；
Figure 11 is the nucleus magnetic hydrogen spectrum figure of compound 2f；
Figure 12 is the nuclear-magnetism carbon spectrogram of compound 2f, and Figure 11 and Figure 12 show that compound 2f structure is correct；
Figure 13 is the nucleus magnetic hydrogen spectrum figure of compound 2g；
Figure 14 is the nuclear-magnetism carbon spectrogram of compound 2g, and Figure 13 and Figure 14 show that compound 2g structure is correct；
Figure 15 is the nucleus magnetic hydrogen spectrum figure of compound 2h；
Figure 16 is the nuclear-magnetism carbon spectrogram of compound 2h, and Figure 15 and Figure 16 show that compound 2h structure is correct.
Specific embodiment
In order to make the foregoing objectives, features and advantages of the present invention clearer and more comprehensible, right combined with specific embodiments below
A specific embodiment of the invention is described in detail.
In the following description, numerous specific details are set forth in order to facilitate a full understanding of the present invention, but the present invention can be with
Implemented using other than the one described here other way, those skilled in the art can be without prejudice to intension of the present invention
In the case of do similar popularization, therefore the present invention is not limited by the specific embodiments disclosed below.
Embodiment 1
25mL round-bottomed flask is taken, 5mL methyl tertiary butyl ether(MTBE), eneyne 1a (107.2mg, 0.5mmol), (acetonitrile) are sequentially added
[(2- biphenyl) di-t-butyl phosphine] hexafluoro-antimonic acid gold (I) (7.8mg, 0.01mmol) confirms raw material by TLC after stirring 1 hour
Total overall reaction is complete to add N- N-iodosuccinimide (225mg, 1mmol).Under normal temperature and pressure, with 500rpm stirring 2 hours.So
It is rotated afterwards using Heidolph Rotary Evaporators, revolving speed 150rpm, temperature is 42 DEG C, vacuum degree 0.06Mpa, when processing
Between be 10min.Again by 200~300 mesh silica gel column chromatographies, eluant, eluent is ethyl acetate: petroleum ether=3: 100, it is isolated
(136.7mg, 0.46mmol, yield 93% also can reflect target product 2a from nuclear magnetic spectrum shape, signal, noise etc.
Product purity is high out).
1H NMR (600MHz, CDCl3): δ 7.62-7.60 (m, 2H), 7.51-7.44 (m, 3H), 6.60 (t, 1H, J=
1.7Hz), 3.86 (dd, 1H, J=19.1,1.5Hz), 3.47 (dd, 1H, J=19.1,2.0Hz), 2.02 (s, 3H)；13C NMR
(150MHz, CDCl3): δ 204.8,167.2,133.1,131.9,129.1,127.0,121.9,51.2,37.7,30.6.
Embodiment 2
25mL round-bottomed flask is taken, 5mL methyl tertiary butyl ether(MTBE), eneyne 1b (151mg, 0.5mmol), (acetonitrile) are sequentially added
[(2- biphenyl) di-t-butyl phosphine] hexafluoro-antimonic acid gold (I) (7.8mg, 0.01mmol) confirms raw material by TLC after stirring 1 hour
Total overall reaction is complete to add N- N-iodosuccinimide (225mg, 1mmol).Under normal temperature and pressure, with 500rpm stirring 3 hours.So
It is rotated afterwards using Heidolph Rotary Evaporators, revolving speed 150rpm, temperature is 42 DEG C, vacuum degree 0.06Mpa, when processing
Between be 10min.Again by 200~300 mesh silica gel column chromatographies, eluant, eluent is ethyl acetate: petroleum ether=5:100, isolated
(176.7mg, 0.46mmol, yield 92% also can reflect target product 2b from nuclear magnetic spectrum shape, signal, noise etc.
Product purity is high out).
1H NMR (600MHz, CDCl3): δ 7.60 (d, 2H, J=7.3Hz), 7.50-7.43 (m, 3H), 6.59 (s, 1H),
4.08 (t, 2H, J=6.3Hz), 3.69 (d, 1H, J=19.2Hz), 3.46 (dd, 1H, J=19.2,1.8Hz), 2.20-2.15
(m, 1H), 2.01 (s, 3H), 1.94-1.88 (m, 1H), 1.74-1.63 (m, 2H)
13C NMR (150MHz, CDCl3): δ 204.2,171.0,167.7,132.9,132.0,129.2,127.0,
122.5,63.6,48.3,44.6,37.9,27.5,21.0.
Embodiment 3
25mL round-bottomed flask is taken, 5mL methyl tertiary butyl ether(MTBE), eneyne 1c (243.8mg, 0.5mmol), (acetonitrile) are sequentially added
[(2- biphenyl) di-t-butyl phosphine] hexafluoro-antimonic acid gold (I) (7.8mg, 0.01mmol) confirms raw material by TLC after stirring 1 hour
Total overall reaction is complete to add N- N-iodosuccinimide (225mg, 1mmol).Under normal temperature and pressure, with 500rpm stirring 2 hours.So
It is rotated afterwards using Heidolph Rotary Evaporators, revolving speed 150rpm, temperature is 42 DEG C, vacuum degree 0.06Mpa, when processing
Between be 10min.Again by 200~300 mesh silica gel column chromatographies, eluant, eluent is ethyl acetate: petroleum ether=20: 100, it is isolated
(245.7mg, 0.43mmol, yield 86% also can reflect target product 2c from nuclear magnetic spectrum shape, signal, noise etc.
Product purity is high out).
1H NMR (600MHz, CDCl3): δ 7.57-7.56 (m, 2H), 7.50-7.49 (m, 1H), 7.47-7.43 (m, 4H),
7.30-7.28 (m, 3H), 7.23 (d, 2H, J=8.0Hz), 7.05-7.03 (m, 2H), 6.55 (t, 1H, J=1.6Hz), 3.63-
3.56 (m, 3H), 3.34 (dd, 1H, J=19.1,1.9Hz), 2.41 (s, 3H), 2.16 (t, 1H, J=10.3Hz), 1.75-
1.69 (m, 2H), 1.58-1.54 (m, 1H)
13C NMR (150MHz, CDCl3): δ 204.1,167.7,143.5,139.0,134.9,132.9,131.9,
129.4,129.1,129.1,128.7,128.0,127.7,127.0,122.4,49.9,48.5,44.7,38.2,27.1,
21.6.
Embodiment 4
25mL round-bottomed flask is taken, 5mL methyl tertiary butyl ether(MTBE), eneyne 1d (141.2mg, 0.5mmol), (acetonitrile) are sequentially added
[(2- biphenyl) di-t-butyl phosphine] hexafluoro-antimonic acid gold (I) (7.8mg, 0.01mmol) confirms raw material by TLC after stirring 1 hour
Total overall reaction is complete to add N- N-iodosuccinimide (225mg, 1mmol).Under normal temperature and pressure, with 500rpm stirring 2 hours.So
It is rotated afterwards using Heidolph Rotary Evaporators, revolving speed 150rpm, temperature is 42 DEG C, vacuum degree 0.06Mpa, when processing
Between be 10min.Again by 200~300 mesh silica gel column chromatographies, eluant, eluent is ethyl acetate: petroleum ether=3: 100, it is isolated
(162.9mg, 0.45mmol, yield 89% also can reflect target product 2d from nuclear magnetic spectrum shape, signal, noise etc.
Product purity is high out).
1H NMR (600MHz, CDCl3): δ 7.64-7.62 (m, 2H), 7.51-7.44 (m, 3H), 6.63 (t, 1H, J=
1.7Hz), 3.55 (qd, 2H, J=19.4,1.9Hz), 2.36 (d, 1H, J=12.8Hz), 2.05-2.00 (m, 1H), 1.89 (d,
1H, J=13.6Hz), 1.65 (dd, 3H, J=10.4,1.4Hz), 1.37-1.11 (m, 4H), 0.89 (qd, 1H, J=11.9,
2.9Hz).
13C NMR (150MHz, CDCl3): δ 204.9,168.0,133.2,131.8,129.1,127.0,123.4,54.2,
46.4,45.0,31.7,27.2,26.6,26.2,25.6.
Embodiment 5
25mL round-bottomed flask is taken, 5mL methyl tertiary butyl ether(MTBE), eneyne 1e (124.4mg, 0.5mmol), (acetonitrile) are sequentially added
[(2- biphenyl) di-t-butyl phosphine] hexafluoro-antimonic acid gold (I) (7.8mg, 0.01mmol) confirms raw material by TLC after stirring 1 hour
Total overall reaction is complete to add N- N-iodosuccinimide (225mg, 1mmol).Under normal temperature and pressure, with 500rpm stirring 2 hours.So
It is rotated afterwards using Heidolph Rotary Evaporators, revolving speed 150rpm, temperature is 42 DEG C, vacuum degree 0.06Mpa, when processing
Between be 10min.Again by 200~300 mesh silica gel column chromatographies, eluant, eluent is ethyl acetate: petroleum ether=3: 100, it is isolated
(138.1mg, 0.42mmol, yield 83% also can reflect target product 2e from nuclear magnetic spectrum shape, signal, noise etc.
Product purity is high out).
1H NMR (600MHz, CDCl3): δ 7.54-7.52 (m, 2H), 7.43-7.42 (m, 2H), 6.54 (t, 1H, J=
1.7Hz), 3.79 (dd, 1H, J=19.1,1.4Hz), 3.41 (dd, 1H, J=19.1,2.0Hz), 1.99 (s, 3H)13C NMR
(150MHz, CDCl3): δ 204.5,165.6,138.0,131.6,129.4,128.2,122.3,51.1,37.3,30.5.
Embodiment 6
25mL round-bottomed flask is taken, 5mL methyl tertiary butyl ether(MTBE), eneyne 1f (132.2mg, 0.5mmol), (acetonitrile) are sequentially added
[(2- biphenyl) di-t-butyl phosphine] hexafluoro-antimonic acid gold (I) (7.8mg, 0.01mmol) confirms raw material by TLC after stirring 1 hour
Total overall reaction is complete to add N- N-iodosuccinimide (225mg, 1mmol).Under normal temperature and pressure, with 500rpm stirring 2 hours.So
It is rotated afterwards using Heidolph Rotary Evaporators, revolving speed 150rpm, temperature is 42 DEG C, vacuum degree 0.06Mpa, when processing
Between be 10min.Again by 200~300 mesh silica gel column chromatographies, eluant, eluent is ethyl acetate: petroleum ether=5: 100, it is isolated
(156.7mg, 0.45mmol, yield 90% also can reflect target product 2f from nuclear magnetic spectrum shape, signal, noise etc.
Product purity is high out).
1H NMR (600MHz, CDCl3): δ 8.02 (s, 1H), 7.91-7.86 (m, 3H), 7.71 (dd, 1H, J=8.6,
1.8Hz), 7.60-7.54 (m, 2H), 6.69 (t, 1H, J=1.7Hz), 3.99 (dd, 1H, J=18.9,1.4Hz), 3.57 (dd,
1H, J=18.9,2.0Hz), 2.05 (s, 3H)
13C NMR (150MHz, CDCl3): δ 204.8,166.9,134.8,132.9,130.4,129.0,128.9,
128.2,127.9,127.3,127.1,123.8,122.2,51.2,37.8,30.7.
Embodiment 7
25mL round-bottomed flask is taken, 5mL methyl tertiary butyl ether(MTBE), eneyne 1g (128.2mg, 0.5mmol), (acetonitrile) are sequentially added
[(2- biphenyl) di-t-butyl phosphine] hexafluoro-antimonic acid gold (I) (7.8mg, 0.01mmol) confirms raw material by TLC after stirring 1 hour
Total overall reaction is complete to add N- N-iodosuccinimide (225mg, 1mmol).Under normal temperature and pressure, with 500rpm stirring 2 hours.So
It is rotated afterwards using Heidolph Rotary Evaporators, revolving speed 150rpm, temperature is 42 DEG C, vacuum degree 0.06Mpa, when processing
Between be 10min.Again by 200~300 mesh silica gel column chromatographies, eluant, eluent is ethyl acetate: petroleum ether=5: 100, it is isolated
(98.7mg, 0.29mmol, yield 58% also can reflect target product 2g from nuclear magnetic spectrum shape, signal, noise etc.
Product purity is high out).
1H NMR (600MHz, C6D6): δ 7.18-7.15 (m, 2H), 7.09 (t, 1H, J=7.4Hz), 6.97 (d, 2H, J=
7.2Hz), 5.65 (s, 1H), 2.79 (d, 1H, J=19.4Hz), 2.26 (t, 2H, J=7.5Hz), 2.13 (dd, 1H, J=
20.3,0.8Hz), 1.66 (s, 3H), 1.62-1.59 (m, 2H), 1.38-1.33 (m, 2H)；
13C NMR (150MHz, C6D6): δ 203.3,173.6,141.2,128.4 (d, 2C, J=10.3Hz), 126.1,
123.8,53.0,38.0,35.1,31.8,29.8,27.8.
Embodiment 8
25mL round-bottomed flask is taken, 5mL methyl tertiary butyl ether(MTBE), eneyne 1h (127.2mg, 0.5mmol), (acetonitrile) are sequentially added
[(2- biphenyl) di-t-butyl phosphine] hexafluoro-antimonic acid gold (I) (7.8mg, 0.01mmol) confirms raw material by TLC after stirring 1 hour
Total overall reaction is complete to add N- N-iodosuccinimide (225mg, 1mmol).Under normal temperature and pressure, with 500rpm stirring 2 hours.So
It is rotated afterwards using Heidolph Rotary Evaporators, revolving speed 150rpm, temperature is 42 DEG C, vacuum degree 0.06Mpa, when processing
Between be 10min.Again by 200~300 mesh silica gel column chromatographies, eluant, eluent is ethyl acetate: petroleum ether=3: 100, it is isolated
(93.0mg, 0.28mmol, yield 55% also can reflect target product 2h from nuclear magnetic spectrum shape, signal, noise etc.
Product purity is high out).
1H NMR (600MHz, CDCl3): δ 7.61-7.60 (m, 2H), 7.48-7.46 (m, 3H), 6.50 (s, 1H), 4.01
(dd, 1H, J=9.4,6.5Hz), 2.61-2.57 (m, 1H), 2.38-2.33 (m, 1H), 2.14-2.09 (m, 1H), 1.62-
1.51 (m, 3H), 1.32-1.16 (m, 2H)
13C NMR (150MHz, CDCl3): δ 203.9,173.8,132.7,131.3,129.1,127.3,121.8,54.0,
48.1,36.0,30.7,23.3,20.5.
It can be seen that one kind provided by the present invention synthesizes alpha-iodine for cyclopentene ketone by non-annularity eneyne ester type compound
The method of compound.Entire reaction carries out at normal temperatures and pressures, has easy to operate, mild condition, substrate functional group compatibility
Well, the advantages that product yield high, easily separated catalyst and product.Research and develop alpha-iodine obtained for cyclopentene ketone compounds have compared with
High reactivity can be used as a kind of important organic intermediate and be applied to medicine, pesticide and synthesis of natural products etc.
Field.
It should be noted that the above examples are only used to illustrate the technical scheme of the present invention and are not limiting, although referring to preferable
Embodiment describes the invention in detail, those skilled in the art should understand that, it can be to technology of the invention
Scheme is modified or replaced equivalently, and without departing from the spirit and scope of the technical solution of the present invention, should all be covered in this hair
In bright scope of the claims.
Claims (8)
1. alpha-iodine is for cyclopentene ketone compounds, it is characterised in that: the alpha-iodine is logical for the structure of cyclopentene ketone compounds
Formula:
In formula, R1、R2For group independent, and carbon number is 1~16；
R1For substituent group, including any one in phenyl, naphthalene, halogenophenyl, naphthenic base；
R2For substituent group, including methyl, chain-like alkyl, naphthenic base, carbonyl, ester group, benzenesulfonyl, phenyl, nitrogen-containing heterocycle group
One of or several combinations.
2. synthesis alpha-iodine described in claim 1 is for the method for cyclopentene ketone compounds, it is characterised in that include the following steps:
It is golden (I) first to sequentially add methyl tertiary butyl ether(MTBE), eneyne ester, (acetonitrile) [(2- biphenyl) di-t-butyl phosphine] hexafluoro-antimonic acid, stirring 1 is small
When after by TLC confirmation, raw material total overall reaction is complete adds N- N-iodosuccinimide, stir 2 hours under normal temperature and pressure, then
Target product alpha-iodine is obtained for cyclopentenone by reaction solution concentrated by rotary evaporation, and by silica gel column chromatography.
3. method of the synthesis alpha-iodine for cyclopentene ketone compounds as claimed in claim 1 or 2, it is characterised in that: described
Eneyne ester includes eneyne ester type compound as shown below,
In formula, R1、R2With above-mentioned R1、R2It is corresponding consistent.
4. method of the synthesis alpha-iodine for cyclopentene ketone compounds as claimed in claim 1 or 2, it is characterised in that: described
Concentration of the eneyne ester in methyl tertiary butyl ether(MTBE) is 0.1mol/L.
5. method of the synthesis alpha-iodine for cyclopentene ketone compounds as claimed in claim 1 or 2, it is characterised in that: described
The molar ratio of eneyne ester and (acetonitrile) [(2- biphenyl) di-t-butyl phosphine] hexafluoro-antimonic acid golden (I) is 1: 0.02.
6. method of the synthesis alpha-iodine for cyclopentene ketone compounds as claimed in claim 1 or 2, it is characterised in that: described
The molar ratio of eneyne ester and N- N-iodosuccinimide is 1: 2.
7. method of the synthesis alpha-iodine for cyclopentene ketone compounds as claimed in claim 2, it is characterised in that: the revolving
Revolving speed be 150~300rpm, temperature be 35~45 DEG C, vacuum degree be 0.05~0.09Mpa, the processing time be 5~15min.
8. method of the synthesis alpha-iodine for cyclopentene ketone compounds as claimed in claim 2, it is characterised in that: the silica gel
Column chromatography, using 200~300 mesh column chromatography silica gels, eluant, eluent is ethyl acetate: petroleum ether=1~30: 100.
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| BEATRICE JACQUES等: "Synthesis, Characterization, and Catalytic Activity of Alcohol-Functionalized NHC Gold(I/III) Complexes", 《ORGANOMETALLICS》 * |
| XIANXIAO CHEN等: "Gold(I)-Catalyzed Tandem Cycloisomerization and Fluorination of 1,3(4)-Enyne Esters with NFSI: One-Pot Assembly of 5-Fluoro-Cyclopentenones", 《ADV. SYNTH. CATAL.》 * |
| XU ZHOU等: "fficient catalytic enantioselective Nazarov cyclizations of divinyl ketoesters", 《ORGANIC CHEMISTRY FRONTIERS》 * |
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