CN115304465A - Green method for converting 1, 3-dithiane derivative into carbonyl compound - Google Patents

Green method for converting 1, 3-dithiane derivative into carbonyl compound Download PDF

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CN115304465A
CN115304465A CN202110492534.0A CN202110492534A CN115304465A CN 115304465 A CN115304465 A CN 115304465A CN 202110492534 A CN202110492534 A CN 202110492534A CN 115304465 A CN115304465 A CN 115304465A
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赵国栋
雷海民
王亚欣
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Beijing University of Chinese Medicine
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Abstract

The invention provides a green method for converting a 1, 3-dithiane derivative into a carbonyl compound, belonging to the field of green organic chemistry. The method uses MBr x (M is Fe) 3+ 、Ce 3+ 、Ce 4+ Etc., x is 3-4) is a catalyst, H 2 O 2 As a unique oxidant, active bromine (RBS) is generated in situ under the conditions of neutrality, openness and room temperature and is used as a direct oxidant to quickly complete deprotection reaction of thioacetal (ketone). Catalysts useful in the invention (e.g., ceBr) 3 、FeBr 3 Etc.) oxidizing agent H 2 O 2 The method has the advantages of low cost and easy obtainment of solvents (such as ethanol, n-butanol and the like), short reaction time, mild conditions, wide functional group compatibility, high product yield (75-99%), simple post-treatment and easy operation, is a current method for deprotecting thioaldehyde (ketone) into carbonyl compounds, and has wide application prospect.

Description

Green method for converting 1, 3-dithiane derivative into carbonyl compound
Technical Field
The invention belongs to the technical field of green chemistry and organic synthesis, and particularly relates to a green method for converting a 1, 3-dithiane derivative into a carbonyl compound.
Background
Carbonyl protection is often an essential step in numerous organic synthetic reactions, particularly in the total synthesis of natural products and multifunctional organic compounds. Thioacetals (ketones) are widely used carbonyl protecting groups due to their ease of preparation and high stability under acidic and basic conditions.
There are many methods currently available for the deprotection of 1, 3-dithiane derivatives, for example, stoichiometric or excess amounts of toxic reactants, including mercury (II) and other heavy metal salts; further, there are methods using heterogeneous conditions using various Fe (III) and Cu (II) salts, and other solvent-free methods, etc., but these methods generally require severe reaction conditions. The use of thioacetal (ketone) compounds in complex molecular synthesis is often hampered by the lack of a mild, versatile removal method. Traditionally, the cleavage of thioacetals (ketones) has been achieved mainly by oxidative means or by the action of mercury (II) salts, however, these methods often lead to competing side reactions in the presence of olefins, aromatic rings, easily oxidizable groups and acid sensitive functional groups and cause a certain pollution of the environment.
Therefore, it is important to develop a method for deprotecting thioacetal (ketone) into carbonyl compound, which is green, efficient, easy to operate and generally applicable.
Disclosure of Invention
The object of the present invention was to develop a versatile, green process for the conversion of 1, 3-dithiane derivatives into carbonyl compounds.
The technical scheme adopted by the invention is as follows:
a green process for converting a 1, 3-dithiane derivative to a carbonyl compound:
under the conditions of neutrality, openness and room temperature, the mixture is treated with MBr x (M is Fe) 3+ 、Ce 3+ 、Ce 4+ Etc., x is 3-4) as catalyst, H 2 O 2 As the sole oxidizing agent, the reaction of converting the 1, 3-dithiane derivative into the carbonyl compound is completed in a short time.
The reaction is carried out in a solvent, and the solvent can be methanol, ethanol, n-butanol, acetonitrile, tetrahydrofuran, diethyl ether, dichloromethane, dimethyl tetrahydrofuran, etc.
The reaction substrate is 1, 3-dithiane derivative with different functional groups, such as hydrogen, alkyl, alkenyl, alkynyl, aryl, ester, alicyclic hydrocarbon and other functional groups or furan, pyridine, thiophene, pyrrole and other heterocyclic ring and other different substituents, and can also be common protective groups such as Ac, TBS, THP, bn, boc, TIPS and the like.
The reaction is carried out under the condition of a catalyst, and the catalyst is CeBr 3 、FeBr 3 、CeBr 4 And Ce (NO) 3 ) 3 -KBr、CeCl 3 -KBr、Ce 2 (C 2 O 4 ) 3 -KBr、FeCl 3 -KBr、Fe(NO 3 ) 3 -KBr、Ce(SO 4 ) 2 -KBr or the like metal (Ce) 3+ 、Fe 3+ 、Ce 4+ ) And bromide.
In the specific operation, a scheme is provided: by reacting a 1, 3-dithiane derivative with a catalyst such as FeBr 3 、CeBr 3 Adding 0.01-0.2eq into proper amount of ethanol, stirring, and adding H into the stirred suspension 2 O 2 Aqueous solution (30 wt%,2-10 eq). The reaction mixture was stirred at room temperature for 5-40min. After the reaction is finished, diluted Na is used 2 S 2 O 3 Solution (0.1M) quenched and extracted with ethyl acetate. CollectingThe organic phase and the aqueous phase are extracted 2-3 times with ethyl acetate. And combining organic phases, washing with water, drying with anhydrous sodium sulfate, filtering, and concentrating under reduced pressure to obtain the product.
The invention has the beneficial effects that:
compared with the prior art, the invention has the following advantages and effects:
the invention realizes the first time that MBr is used under the neutral condition x -H 2 O 2 The reaction of converting the 1, 3-dithiane derivative into the carbonyl compound by the in-situ generated RBS catalysis is a green method for removing the carbonyl protecting group in an amplifying way. Compared with the prior method for deprotecting mercaptal (ketone) into carbonyl compound, the method has the characteristics of easily available raw materials, low cost, fast reaction, wide substrate application range, simple route, easy operation, environmental protection and the like, has more advantages than all the prior methods, and has good application prospect.
Drawings
FIGS. 1 and 2 are those of example 1 1 H-NMR and 13 C-NMR spectrum
FIGS. 3 and 4 are those of embodiment 2 1 H-NMR and 13 C-NMR spectrum
FIGS. 5 and 6 are those of embodiment 3 1 H-NMR and 13 C-NMR spectrum
FIGS. 7 and 8 are those of embodiment 4 1 H-NMR and 13 C-NMR spectrum
FIGS. 9 and 10 are those of example 5 1 H-NMR and 13 C-NMR spectrum
FIGS. 11 and 12 are those of embodiment 6 1 H-NMR and 13 C-NMR spectrum
FIGS. 13 and 14 are those of example 7 1 H-NMR and 13 C-NMR spectrum
FIGS. 15 and 16 are those of example 8 1 H-NMR and 13 C-NMR spectrum
FIGS. 17 and 18 are those of embodiment 9 1 H-NMR and 13 C-NMR spectrum
FIGS. 19 and 20 are those of example 10 1 H-NMR and 13 C-NMR spectrum
FIGS. 21 and 22 are those of example 11 1 H-NMR and 13 C-NMR spectrum
FIGS. 23 and 24 are those of example 12 1 H-NMR and 13 C-NMR spectrum
Detailed Description
The present invention will be described in more detail with reference to specific embodiments, but the scope of the present invention is not limited thereto.
In the following examples 1 H-NMR and 13 the C-NMR spectra were measured at room temperature and recorded on a 400MHz spectrometer, 1 the H is 400MHz, and the total frequency of the hydrogen is, 13 c was 100MHz and the spectrometer was from brueck corporation.
Example 1
Figure BSA0000241214510000041
40ml of ethanol and 1a (4 mmol, 1g) are sequentially added into a 100ml round-bottom flask, the mixture is stirred uniformly, and then CeBr is sequentially added into the mixture of the ethanol and the 1a 3 (0.32mmol，0.122g)，H 2 O 2 The aqueous solution (30 wt%,12mmol, 1.23ml) was stirred at room temperature for 10min. After the reaction is finished, na is used 2 S 2 O 3 The reaction was quenched with a solution (0.1M, 60mL) and extracted with ethyl acetate (100 mL). The organic phase was collected and the aqueous phase was extracted with ethyl acetate (2 × 50 mL). The organic phases were combined, washed with water, dried over anhydrous sodium sulfate, filtered and concentrated under reduced pressure to obtain the desired product 1b (yield: 95%). The characterization data for this compound are as follows: 1 H-NMR(400MHz，CDCl 3 )δ2.37(t，J＝7.5Hz，4H)，1.66-1.47(m，4H)，1.40-1.16(m，8H)，0.87(t，J＝7.1Hz，6H). 13 C-NMR(100MHz，CDCl 3 )δ211.82(s)，42.90(s)，31.58(s)，23.70(s)，22.59(s)，14.04(s).
example 2
Figure BSA0000241214510000042
40ml of ethanol and 2a (4 mmol, 1g) were sequentially added to a 100ml round-bottom flask, stirred well, and then added to bothSequentially adding CeBr into the mixture 3 (0.32mmol，0.122g)，H 2 O 2 An aqueous solution (30 wt%,12mmol, 1.23ml) was stirred at room temperature for 10min. After the reaction is finished, na is used 2 S 2 O 3 The reaction was quenched with a solution (0.1M, 60mL) and extracted with ethyl acetate (100 mL). The organic phase was collected and the aqueous phase was extracted with ethyl acetate (2 × 50 mL). The organic phases are combined and washed with water, dried over anhydrous sodium sulfate, filtered and concentrated under reduced pressure to obtain the target product 2b (yield: 87%). The characterization data for this compound are as follows: 1 H-NMR(400MHz，CDCl 3 )δ8.46(s，1H)，8.03(dd，J＝8.6，1.7Hz，1H)，7.96(d，J＝8.0Hz，1H)，7.88(dd，J＝8.1，5.7Hz，2H)，7.66-7.51(m，2H)，2.72(s，3H). 13 C-NMR(100MHz，CDCl 3 )δ198.20(s)，135.70(s)，134.61(s)，132.63(s)，130.30(s)，129.66(s)，128.55(d，J＝5.2Hz)，127.89(s)，126.88(s)，124.01(s)，26.79(s).
example 3
Figure BSA0000241214510000051
50ml of ethanol and 3a (5mmol, 1.1g) were sequentially added to a 100ml round-bottom flask, and the mixture was stirred well, and then CeBr was sequentially added to the mixture 3 (0.4mmol，0.152g)，H 2 O 2 The aqueous solution (30 wt%,15mmol, 1.53ml) was stirred at room temperature for 10min. After the reaction is finished, na is used 2 S 2 O 3 The reaction was quenched with a solution (0.1M, 75mL) and extracted with ethyl acetate (100 mL). The organic phase was collected and the aqueous phase was extracted with ethyl acetate (2 × 50 mL). The organic phases are combined and washed with water, dried over anhydrous sodium sulfate, filtered and concentrated under reduced pressure to obtain the target product 3b (yield: 92%). The characterization data for this compound are as follows: 1 H-NMR(400MHz，CDCl 3 )δ7.70(dd，J＝3.8，1.1Hz，1H)，7.63(dd，J＝5.0，1.1Hz，1H)，7.13(dd，J＝4.9，3.8Hz，1H)，2.57(s，3H). 13 C-NMR(100MHz，CDCl 3 )δ190.86(s)，144.74(s)，133.90(s)，132.58(s)，128.24(s)，27.08(s).
example 4
Figure BSA0000241214510000052
40ml of ethanol and 4a (4 mmol, 1.1g) are sequentially added into a 100ml round-bottom flask, the mixture is stirred uniformly, and then CeBr is sequentially added into the mixture 3 (0.32mmol，0.122g)，H 2 O 2 The aqueous solution (30 wt%,12mmol, 1.23ml) was stirred at room temperature for 10min. After the reaction is finished, na is used 2 S 2 O 3 The reaction was quenched with a solution (0.1M, 60mL) and extracted with ethyl acetate (100 mL). The organic phase was collected and the aqueous phase was extracted with ethyl acetate (2 × 50 mL). The organic phases were combined, washed with water, dried over anhydrous sodium sulfate, filtered and concentrated under reduced pressure to obtain the desired product 4b (yield: 97%). The characterization data for this compound are as follows: 1 H-NMR(400MHz，CDCl 3 )δ7.80(dd，J＝5.2，3.3Hz，1H)，7.63-7.55(m，1H)，7.48(dd，J＝10.5，4.7Hz，1H). 13 C-NMR(100MHz，CDCl 3 )δ196.84(s)，137.71(s)，132.52(s)，130.16(s)，128.38(s).
example 5
Figure BSA0000241214510000061
40ml of ethanol and 5a (4 mmol, 0.95g) are sequentially added into a 100ml round-bottom flask, the mixture is stirred uniformly, and then CeBr is sequentially added into the mixture 3 (0.32mmol，0.122g)，H 2 O 2 The aqueous solution (30 wt%,12mmol, 1.23ml) was stirred at room temperature for 10min. After the reaction is finished, na is used 2 S 2 O 3 The reaction was quenched with a solution (0.1M, 60mL) and extracted with ethyl acetate (100 mL). The organic phase was collected and the aqueous phase was extracted with ethyl acetate (2 × 50 mL). The organic phases were combined, washed with water, dried over anhydrous sodium sulfate, filtered and concentrated under reduced pressure to obtain the desired product 5b (yield: 81%). The characterization data for this compound are as follows: 1 H-NMR(400MHz，CDCl 3 )δ8.14-7.98(m，1H)，7.46(td，J＝7.5，1.4Hz，1H)，7.39-7.10(m，2H)，2.96(t，J＝6.1Hz，2H)，2.84-2.55(m，2H)，2.14(dt，J＝12.6，6.4Hz，2H). 13 C-NMR(100MHz，CDCl 3 )δ198.48(s)，144.59(s)，133.49(s)，132.72(s)，128.87(s)，127.26(s)，126.72(s)，39.27(s)，29.81(s)，23.39(s).
example 6
Figure BSA0000241214510000062
40ml of ethanol and 6a (4 mmol, 0.96g) are sequentially added into a 100ml round-bottom flask, the mixture is stirred evenly, and then CeBr is sequentially added into the mixture of the ethanol and the 6a 3 (0.32mmol，0.122g)，H 2 O 2 The aqueous solution (30 wt%,12mmol, 1.23ml) was stirred at room temperature for 10min. After the reaction is finished, na is used 2 S 2 O 3 The reaction was quenched with solution (0.1M, 60mL) and extracted with ethyl acetate (100 mL). The organic phase was collected and the aqueous phase was extracted with ethyl acetate (2 × 50 mL). The organic phases were combined, washed with water, dried over anhydrous sodium sulfate, filtered and concentrated under reduced pressure to obtain the desired product 6b (yield: 78%). The characterization data for this compound are as follows: 1 H-NMR(400MHz，CDCl 3 )δ8.13-7.83(m，2H)，7.11-6.68(m，2H)，3.87(s，3H)，2.55(s，3H). 13 C-NMR(100MHz，CDCl 3 )δ196.91(s)，163.62(s)，130.72(s)，130.49(s)，113.81(s)，55.60(s)，26.47(s).
example 7
Figure BSA0000241214510000071
40ml of ethanol and 7a (4 mmol, 1.1g) are sequentially added into a 100ml round-bottom flask, the mixture is stirred uniformly, and then CeBr is sequentially added into the mixture of the ethanol and the 7a 3 (0.32mmol，0.122g)，H 2 O 2 An aqueous solution (30 wt%,12mmol, 1.23ml) was stirred at room temperature for 10min. After the reaction is finished, na is used 2 S 2 O 3 The reaction was quenched with a solution (0.1M, 60mL) and extracted with ethyl acetate (100 mL). The organic phase was collected and the organic phase was,the aqueous phase was extracted with ethyl acetate (2 × 50 mL). The organic phases were combined, washed with water, dried over anhydrous sodium sulfate, filtered and concentrated under reduced pressure to obtain the desired product 7b (yield: 75%). The characterization data for this compound are as follows: 1 H-NMR(400MHz，CDCl 3 )δ7.99(d，J＝8.7Hz，1H)，7.19(d，J＝8.7Hz，1H)，2.59(s，2H)，2.32(s，2H). 13 C-NMR(100MHz，CDCl 3 )δ196.90(s)，168.93(s)，154.43(s)，134.81(s)，130.02(s)，121.85(s)，26.66(s)，21.21(s).
example 8
Figure BSA0000241214510000081
30ml of ethanol and 8a (3 mmol, 0.95g) were sequentially added to a 100ml round-bottom flask, stirred well, and CeBr was sequentially added to the mixture 3 (0.24mmol，0.091g)，H 2 O 2 An aqueous solution (30 wt%,9mmol, 0.92ml) was stirred at room temperature for 10min. After the reaction is finished, na is used 2 S 2 O 3 The reaction was quenched with a solution (0.1M, 45mL) and extracted with ethyl acetate (100 mL). The organic phase was collected and the aqueous phase was extracted with ethyl acetate (2 × 50 mL). The organic phases were combined, washed with water, dried over anhydrous sodium sulfate, filtered and concentrated under reduced pressure to obtain the desired product 8b (yield: 82%). The characterization data for this compound are as follows: 1 H-NMR(400MHz，CDCl 3 )δ8.05-7.83(m，2H)，7.54-7.28(m，5H)，7.11-6.89(m，2H)，5.13(s，2H)，2.55(s，3H). 13 C-NMR(100MHz，CDCl 3 )δ196.83(s)，162.71(s)，136.28(s)，130.66(d，J＝6.8Hz)，128.79(s)，128.34(s)，127.56(s)，114.64(s)，70.22(s)，26.44(s).
example 9
Figure BSA0000241214510000082
40ml of ethanol and 9a (4 mmol, 1.1g) are sequentially added into a 100ml round-bottom flask, the mixture is stirred uniformly, and then CeBr is sequentially added into the mixture 3 (0.32mmol，0.122g)，H 2 O 2 An aqueous solution (30 wt%,12mmol, 1.23ml) was stirred at room temperature for 10min. After the reaction is finished, na is used 2 S 2 O 3 The reaction was quenched with solution (0.1M, 60mL) and extracted with ethyl acetate (100 mL). The organic phase was collected and the aqueous phase was extracted with ethyl acetate (2 × 50 mL). The organic phases were combined, washed with water, dried over anhydrous sodium sulfate, filtered and concentrated under reduced pressure to obtain the desired product 9b (yield: 96%). The characterization data for this compound are as follows: 1 H-NMR(400MHz，CDCl 3 )δ7.65(d，J＝7.3Hz，2H)，7.48(ddd，J＝8.9，8.4，4.0Hz，4H)，7.35-7.20(m，2H). 13 C-NMR(100MHz，CDCl 3 )δ194.04(s)，144.56(s)，134.80(s)，134.28(s)，129.20(s)，124.44(s)，120.43(s).
example 10
Figure BSA0000241214510000091
40ml of ethanol and 10a (4 mmol, 1g) are sequentially added into a 100ml round-bottom flask, the mixture is stirred uniformly, and then CeBr is sequentially added into the mixture 3 (0.32mmol，0.122g)，H 2 O 2 The aqueous solution (30 wt%,12mmol, 1.23ml) was stirred at room temperature for 10min. After the reaction is finished, na is used 2 S 2 O 3 The reaction was quenched with a solution (0.1M, 60mL) and extracted with ethyl acetate (100 mL). The organic phase was collected and the aqueous phase was extracted with ethyl acetate (2 × 50 mL). The organic phases were combined and washed successively with water, dried over anhydrous sodium sulfate, filtered and concentrated under reduced pressure to obtain the desired product 10b (yield: 89%). The characterization data for this compound are as follows: 1 H-NMR(400MHz，CDCl 3 )δ10.11(s，1H)，8.27(s，1H)，7.90(ddd，J＝25.8，13.7，8.6Hz，4H)，7.68-7.43(m，2H). 13 C-NMR(100MHz，CDCl 3 )δ192.24(s)，136.45(s)，134.56(s)，134.12(s)，132.65(s)，129.55(s)，129.12(d，J＝4.0Hz)，128.10(s)，127.12(s)，122.75(s).
example 11
Figure BSA0000241214510000092
40ml of ethanol and 11a (4 mmol, 1g) are sequentially added into a 100ml round-bottom flask, the mixture is stirred uniformly, and then CeBr is sequentially added into the mixture of the ethanol and the 11a 3 (0.32mmol，0.122g)，H 2 O 2 An aqueous solution (30 wt%,12mmol, 1.23ml) was stirred at room temperature for 10min. After the reaction is finished, na is used 2 S 2 O 3 The reaction was quenched with a solution (0.1M, 60mL) and extracted with ethyl acetate (100 mL). The organic phase was collected and the aqueous phase was extracted with ethyl acetate (2 × 50 mL). The combined organic phases were washed with water, dried over anhydrous sodium sulfate, filtered and concentrated under reduced pressure to obtain the desired product 11b (yield: 83%). The characterization data for this compound are as follows: 1 H-NMR(400MHz，CDCl 3 )δ9.81(s，1H)，7.49-7.33(m，2H)，6.94(d，J＝8.2Hz，1H)，3.92(d，J＝10.7Hz，6H). 13 C-NMR(100MHz，CDCl 3 )δ190.96(s)，154.49(s)，149.61(s)，130.13(s)，126.94(s)，110.40(s)，108.88(s)，56.12(d，J＝19.1Hz).
example 12
Figure BSA0000241214510000101
40ml of ethanol and 12a (4 mmol, 0.95g) are sequentially added into a 100ml round-bottom flask, the mixture is stirred uniformly, and then CeBr is sequentially added into the mixture 3 (0.32mmol，0.122g)，H 2 O 2 The aqueous solution (30 wt%,12mmol, 1.23ml) was stirred at room temperature for 10min. After the reaction is finished, na is used 2 S 2 O 3 The reaction was quenched with a solution (0.1M, 60mL) and extracted with ethyl acetate (100 mL). The organic phase was collected and the aqueous phase was extracted with ethyl acetate (2 × 50 mL). The organic phases were combined, washed with water, dried over anhydrous sodium sulfate, filtered and concentrated under reduced pressure to obtain the desired product 12b (yield: 75%). The characterization data for this compound are as follows: 1 H-NMR(400MHz，CDCl 3 )δ9.80(s，1H)，7.88-7.50(m，2H)，6.85(d，J＝8.2Hz，1H)，4.66(t，J＝8.8Hz，2H)，3.24(t，J＝8.8Hz，2H). 13 C-NMR(100MHz，CDCl 3 )δ190.71(s)，165.70(s)，133.05(s)，130.46(s)，128.51(s)，125.96(s)，109.66(s)，72.48(s)，28.80(s).

Claims (9)

1. a green process for converting a 1, 3-dithiane derivative to a carbonyl compound, said process comprising: under the conditions of neutrality, open air and room temperature, 1, 3-dithiane derivatives with different functional groups are used as reaction substrates, wherein R1 and R2 can be different functional groups such as hydrogen radical, alkyl, alkenyl, alkynyl, aryl, ester group, alicyclic hydrocarbon and the like or different substituent groups such as furan, pyridine, thiophene, pyrrole and other heterocycles and the like, and can also be common protective groups such as Ac, TBS, THP, bn, boc, TIPS and the like, and MBr is used as a substrate x (M is Fe) 3+ 、Ce 3+ 、Ce 4+ Etc., x is 3-4) as catalyst, H 2 O 2 As the only oxidant, the reaction for converting the 1, 3-dithiane derivative into the carbonyl compound is completed in a short time.
Figure FSA0000241214500000011
2. The method of claim 1, wherein: the reaction is carried out under the condition of a catalyst, and the catalyst is CeBr 3 、FeBr 3 、CeBr 4 And Ce (NO) 3 ) 3 -KBr、CeCl 3 -KBr、Ce 2 (C 2 O 4 ) 3 -KBr、FeCl 3 -KBr、Fe(NO 3 ) 3 -KBr、Ce(SO 4 ) 2 -KBr or the like metal (Ce) 3+ 、Fe 3+ 、Ce 4+ ) And bromide, in a molar ratio of catalyst to 1, 3-dithiane derivative of 0.01-0.2: 1.
3. The method of claim 1, wherein: h 2 O 2 Is the only oxidant, and has a concentration of 3-30%, H 2 O 2 And (2) the reaction product of (1),the molar ratio of the 3-dithiane derivative is 2-10: 1.
4. The method of claim 1, wherein: the reaction is carried out in a solvent, the solvent can be methanol, ethanol, n-butanol, acetonitrile, tetrahydrofuran, diethyl ether, dichloromethane, dimethyl tetrahydrofuran, etc., and the ratio of the 1, 3-dithiane derivative to the solvent is 1mmol/10-20ml.
5. The method of claim 1, wherein: the reaction temperature was room temperature.
6. The method of claim 1, wherein: the reaction can be carried out under the condition of not excluding air and moisture, namely, under the open condition; the reaction is carried out at a neutral pH.
7. The method of claim 1, wherein: the preferred reaction time is 5-40min.
8. The method of claim 1, wherein: in the specific operation, 1, 3-dithiane derivative and catalyst are added into a proper amount of solvent and stirred uniformly, and then H is added into the stirred suspension 2 O 2 The aqueous solution and the reaction mixture are continuously stirred and reacted for 5 to 40min at room temperature to complete the reaction of converting the 1, 3-dithiane derivative into the carbonyl compound.
9. The method of claim 1, wherein: the reaction for deprotecting the mercaptal (ketone) to carbonyl compound is carried out by diluting with Na 2 S 2 O 3 Quenching the solution, extracting with organic solvent such as ethyl acetate, collecting organic phase, extracting water phase with organic solvent for 2-3 times, mixing organic phases, sequentially washing with water, drying with anhydrous sodium sulfate, filtering, and concentrating under reduced pressure to obtain carbonyl compound.
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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110256315A (en) * 2018-03-12 2019-09-20 兰州大学 A method of preparing Sulfide-containing Hindered formyl thioester conjugate
CN112778257A (en) * 2021-01-21 2021-05-11 香港科技大学 Green method for oxidizing furfuryl alcohol into dihydropyrone derivative
CN112939749A (en) * 2021-02-22 2021-06-11 香港科技大学 Green bromination method
CN113024438A (en) * 2021-02-22 2021-06-25 香港科技大学 Green method for preparing oxindole derivative

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110256315A (en) * 2018-03-12 2019-09-20 兰州大学 A method of preparing Sulfide-containing Hindered formyl thioester conjugate
CN112778257A (en) * 2021-01-21 2021-05-11 香港科技大学 Green method for oxidizing furfuryl alcohol into dihydropyrone derivative
CN112939749A (en) * 2021-02-22 2021-06-11 香港科技大学 Green bromination method
CN113024438A (en) * 2021-02-22 2021-06-25 香港科技大学 Green method for preparing oxindole derivative

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
AHMED KAMAL等: "A Mild and Efficient Dethioacetalization Employing FeCl3Σ6H2O: Synthesis of DNA-binding Pyrrolo[2,1-c][1,4]benzodiazepine Ring System and its Dimers" *
EJABUL MONDAL等: "An exceptionally simple and catalytic method for regeneration of carbonyl functionality from the corresponding 1,3-oxathiolanes" *

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