KR101777923B1 - SYNTHESIZING METHOD OF α-TERTIARY ARYL KETONE - Google Patents

SYNTHESIZING METHOD OF α-TERTIARY ARYL KETONE Download PDF

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KR101777923B1
KR101777923B1 KR1020150165713A KR20150165713A KR101777923B1 KR 101777923 B1 KR101777923 B1 KR 101777923B1 KR 1020150165713 A KR1020150165713 A KR 1020150165713A KR 20150165713 A KR20150165713 A KR 20150165713A KR 101777923 B1 KR101777923 B1 KR 101777923B1
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aryl
aldehyde
synthesizing
aryl ketone
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류도현
강병철
남동국
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성균관대학교산학협력단
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
    • C07C45/67—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton
    • C07C45/68—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
    • C07C45/72—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms by reaction of compounds containing >C = O groups with the same or other compounds containing >C = O groups
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    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/12—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides
    • B01J31/14—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides of aluminium or boron
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
    • C07C45/67—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton
    • C07C45/68—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
    • C07C45/72—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms by reaction of compounds containing >C = O groups with the same or other compounds containing >C = O groups
    • C07C45/75—Reactions with formaldehyde
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C49/00—Ketones; Ketenes; Dimeric ketenes; Ketonic chelates
    • C07C49/20—Unsaturated compounds containing keto groups bound to acyclic carbon atoms
    • C07C49/213—Unsaturated compounds containing keto groups bound to acyclic carbon atoms containing six-membered aromatic rings

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Abstract

The method of synthesizing? -Tricarylketone according to the present invention comprises reacting an aryldeazoalkane with an aldehyde (Aldehyde) in the presence of a chiral boron Lewis acid catalyst to produce? -Tertiary aryl ketones.

Description

TECHNICAL FIELD The present invention relates to a method for synthesizing an α-tertiary aryl ketone,

More particularly, the present invention relates to a method for synthesizing an enantioenriched acyclic aliphatic-tertiary aryl ketone.

alpha-aryl ketones and cycloalkanones are building blocks useful for the synthesis of natural products and pharmaceuticals. Due to the ubiquity and utility of α-aryl ketones and cycloalkanes, the development of transition-metal catalyzed α-aryl reactions has attracted considerable interest over the last several decades. Although the enantioselective catalytic structures of the alpha-tertiary arylalkanone and cycloalkanone are successful pioneering studies on enantioselective alpha-arylation that generate chiral quaternary carbon centers, the transition- Have recently been discovered due to racemization in products associated with metal-catalyzed? -Arylation methods.

Various methods for solving the manufacturing process of acyclic aliphatic alpha-tertiary aryl ketones, such as the non-cyclic Kumada and Negishi cross-coupling reactions to provide an optically active alpha-tertiary aryl ketone, , Nickel-bis (oxazoline) -catalized reductive acrylic cross-coupling reactions in the presence of manganese, and the like. Also complementarily, enantioselective protonation of gold-catalyzed enol silanes has been developed, but there are problems such as limited substrate coverage and low yields from homocoupling.

Therefore, there is a need for the development of a new, highly efficient, enantioselective catalyst method.

It is an object of the present invention to provide a process for the synthesis of an alpha-tertiary aryl ketone exhibiting high optical activity.

The process for synthesizing an alpha-tertiary aryl ketone for the purpose of the present invention comprises reacting an aldehyde (Aldehyde) with an aryldiazoalkane under a chiral boron Lewis acid catalyst to produce an alpha-tertiary aryl ketone (α-tertiary aryl ketones).

In one embodiment, the chiral boron Lewis acid catalyst may be a compound represented by the following formula (1).

[Chemical Formula 1]

Figure 112015115213575-pat00001

In formula (1), Ar and R each represent an aryl group, and X represents Tf 2 N or TfO.

At this time, the chiral boron Lewis acid catalyst may be activated by triflic acid.

In one embodiment, the chiral boron Lewis acid catalyst can be used at a concentration of 20 mol%.

In one embodiment, the aryldiazoalkane may be represented by the following formula (2).

(2)

Figure 112015115213575-pat00002

In formula (2), Ar 1 and R 1 each represent an aryl group or an alkyl group.

In one embodiment, the aldehyde may be at least one of an aromatic aldehyde compound or an aliphatic aldehyde compound.

The aldehyde may be an aromatic aldehyde compound, and the chiral boron Lewis acid catalyst may be a compound represented by the following formula (1d).

≪ RTI ID = 0.0 &

Figure 112015115213575-pat00003

The aldehyde may be an aliphatic aldehyde compound, and the chiral boron Lewis acid catalyst may be a compound represented by the following formula (1e).

[Formula 1e]

Figure 112015115213575-pat00004

In one embodiment, 0.30 mmol to 0.40 mmol of the aryl diazoalkane and 0.20 mmol to 0.30 mmol of the aldehyde can be reacted.

At this time, the aryldiazoalkane and the aldehyde can be reacted at -85 ° C to 0 ° C for 20 minutes to 130 minutes.

According to the process for synthesizing? -Tricaryl ketone of the present invention, it is possible to provide an excellent yield and high optically active acyclic? -Cyclic aryl ketone. The α-tertiary aryl ketone of the present invention can utilize various aryl diazo alkanes and aldehydes, and α-tertiary aryl ketones having high optical purity can be efficiently synthesized according to the synthesis method of the present invention.

FIG. 1 is a view for explaining a method of synthesizing? -Citalarylketone according to an embodiment of the present invention.

Hereinafter, embodiments of the present invention will be described in detail with reference to the accompanying drawings. The present invention is capable of various modifications and various forms, and specific embodiments are illustrated in the drawings and described in detail in the text. It is to be understood, however, that the invention is not intended to be limited to the particular forms disclosed, but on the contrary, is intended to cover all modifications, equivalents, and alternatives falling within the spirit and scope of the invention. Like reference numerals are used for like elements in describing each drawing.

The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. The singular expressions include plural expressions unless the context clearly dictates otherwise. In the present application, the term "comprises" or "having ", etc. is intended to specify that there is a feature, step, operation, element, part or combination thereof described in the specification, , &Quot; an ", " an ", " an "

Unless defined otherwise, all terms used herein, including technical or scientific terms, have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Terms such as those defined in commonly used dictionaries are to be interpreted as having a meaning consistent with the contextual meaning of the related art and are to be interpreted as either ideal or overly formal in the sense of the present application Do not.

The method of synthesizing? -Tricarylketone according to the present invention comprises reacting an aryldeazoalkane with an aldehyde (Aldehyde) in the presence of a chiral boron Lewis acid catalyst to obtain an optically active acyclic? Synthesis of α-tertiary aryl ketones.

The chiral boron Lewis acid catalyst may be an oxazaborolidinium compound represented by the following formula (1), or may be activated by triflic acid.

[Chemical Formula 1]

Figure 112015115213575-pat00005

In formula (1), Ar and R each represent an aryl group, and X represents Tf 2 N or TfO.

In the present invention, the "aryl group" is a monovalent substituent derived from an aromatic hydrocarbon, and includes a phenyl group, a naphtyl group, an anthracenyl group, a phenanthryl group, a naphthacenyl group a naphthacenyl group, a pyrenyl group, a perylene group, a tolyl group, a biphenylyl group, and a terphenyl group. The aryl group may be substituted or unsubstituted.

In Formula 1, Ar represents phenyl or 3,5-dimethylphenyl, R represents phenyl, 2- (trifluoromethyl) phenyl, or o -tolyl, X may be TF 2 N or TFO have.

The chiral boron Lewis acid catalyst may be used in a concentration of 20 mol%.

0.30 mmol to 0.40 mmol of the aryldiazoalkane and 0.20 mmol to 0.30 mmol of the aldehyde can be reacted in the presence of the catalyst and the reaction can be carried out at -85 ° C to 0 ° C for 20 minutes to 130 minutes .

The aryldiazoalkane may be represented by the following general formula (2).

(2)

Figure 112015115213575-pat00006

In formula (2), Ar 1 and R 1 each represent an aryl group or an alkyl group.

Since the aryl group is substantially the same as that described above, a detailed description thereof will be omitted. The alkyl group is a monovalent substituent derived from an aliphatic saturated hydrocarbon, and examples thereof include a methyl group, an ethyl group, and a propyl group.

In addition, the aldehyde may be an aromatic aldehyde compound or an aliphatic aldehyde compound.

Aldehyde means a compound in which two hydrogen atoms are lost at the end of a hydrocarbon chain, and instead, one oxygen atom is bonded by a double bond, that is, a compound having an aldehyde group (-CHO).

The aromatic aldehyde compound is a compound having an aromatic ring substituted with an aldehyde, and examples thereof include benzaldehyde and naphthaldehyde. The aliphatic aldehyde compound is an aldehyde having a non-aromatic carbon ring compound such as n-heptyl aldehyde, n-capryl aldehyde, n-decyl aldehyde, etc. .

For example, when the aldehyde is an aromatic aldehyde compound, the chiral boron Lewis acid catalyst may be a compound represented by the following formula (1d). At this time, the reaction time may be 30 minutes.

≪ RTI ID = 0.0 &

Figure 112015115213575-pat00007

In addition, when the aldehyde is an aliphatic aldehyde compound, the chiral boron Lewis acid catalyst may be a compound represented by the following formula (1e). At this time, the reaction time may be 2 hours.

[Formula 1e]

Figure 112015115213575-pat00008

In the method of synthesizing an? -Cycloaryl ketone of the present invention, the aryldiazoalkane and the aldehyde can be used without limitation, and are not limited by the aryldiazoalkane and the aldehyde described above.

More specifically, a method for synthesizing an? -Citalaryl ketone of the present invention will now be described. A transition-metal free coupling capable of providing an optically active non-cyclic? -Cyclic aryl ketone using an aryl diazoalkane of the present invention As a reaction, a method for synthesizing an? -Cicarylketone according to an embodiment of the present invention can be illustrated as shown in the following Reaction Scheme 1.

[Reaction Scheme 1]

Figure 112015115213575-pat00009

Referring to Scheme 1, in the presence of a chiral boron Lewis acid catalyst, an aryl diazoalkane is asymmetrically injected asymmetrically into the aryl group of the aldehyde between the CH bonds of the aldehyde, resulting in selective 1, A non-cyclic -c-tertiary aryl ketone having an optically active optical activity with excellent optical activity can be synthesized by 2-hybrid movement. Optical activity refers to optical rotation, in which a material rotates the plane of polarization of plane polarized light to the right or left.

Hereinafter, with reference to FIG. 1, the synthesis of? -Tricaryl ketones according to the embodiments of the present invention in the presence of the catalyst represented by the above-described Formula 1d and Formula 1e will be described.

FIG. 1 is a view for explaining a method of synthesizing? -Citalarylketone according to an embodiment of the present invention.

Figure 1 shows a transition-state model in the presence of catalysts 1d and 1e.

Referring to FIG. 1, the coordination modes of the aldehydes of catalysts 1d and 1e are enantioselective cyanosilylation, 1,3-dipolar cycloaddition, cyclized propanation, and Roskamp The same as observed in the reaction. In the pre-charged state (4), the aldehyde group is located on the mexyl group, which effectively protects the re (rear) from attack by the aryl diazoalkane. Due to the steric interactions between the boron Ar substituent of the catalyst and the phenyl group of the aryldiazoalkane, the aryldiazoalkane approaches the aldehyde for nucleophilic addition to the phenyl group located remotely from the aldehyde group. For aromatic aldehydes in which R is an aryl group, the possible π-π interaction between the aryl ring of the aromatic aldehyde and the aryl diazoalkanaryl group together hold the two aryl rings together. The nucleophilic addition of the aryl diazoalkane from the si face (front) of the aldehyde leads to intermediate (5). At this time, the enantiomeric alpha-tertiary aryl ketone (2), the major product of this reaction, is provided by chemoselective 1,2-hydride shift with loss of nitrogen.

Thus, an alpha-tertiary aryl ketone having an excellent yield and optical activity can be synthesized through the synthesis of alpha-tertiary aryl ketone of the present invention

Further, the optically active? -Trimeric aryl ketone can be chemically modified and functionalized. The functionalization of the alpha-tertiary aryl ketone can be represented, for example, as shown in Reaction Scheme 2 below. In Scheme 2, 2s represents an a-tertiary aryl ketone synthesized according to one embodiment of the present invention.

[Reaction Scheme 2]

Figure 112015115213575-pat00010

Referring to Scheme 2, reduction of 2s with L-Selectride can lead to highly optically enriched secondary alcohol 6a. In addition, reductive amination of 2s with sodium triacetoxyborohydride can provide a secondary amine (7) with conservation of ee.

That is, the α-tertiary aryl ketone according to the synthesis method of α-tertiary aryl ketone of the present invention can be easily changed into secondary alcohol and amine having optical activity without loss of optical purity, It means usability.

Example 1

In order to confirm the synthesis of? -Tricarylketone according to various oxazaboroluridinium catalyst conditions, 1-phenyldiazoethane was used as the aryldiazoalkane and benzaldehyde as the aldehyde according to the following reaction scheme 3, Α-tertiary aryl ketone (hereinafter referred to as 2a) according to Examples 1-1 to 1-6 of the present invention was synthesized. 3a represents the product of the minor phenyl transfer.

[Reaction Scheme 3]

Figure 112015115213575-pat00011

As the oxazaborolinium catalyst, the catalysts (1a to 1d) respectively represented by the following general formula (3) were used.

(3)

Figure 112015115213575-pat00012

The reaction was carried out by reacting 1-phenyldiazoethane (0.35 mmol) and benzaldehyde (0.23 mmol) in 1.0 mL of a solvent of 20 mol% concentration of catalyst 1a to 1d respectively at -78 ° C for 30 minutes, Respectively. In Table 1, the ratio of 2a and 3a (2a / 3a) was determined by 1 H NMR analysis, yielding a yield of 2a. ee was determined by chiral HPLC of 2a.

Example 1 menstruum catalyst 2a / 3a yield(%) ee (%) One CH 2 Cl 2 1a 3: 1 60 70 2 toluene 1a 4: 1 69 85 3 toluene 1b 6: 1 85 93 4 toluene 1c 4: 1 73 97 5 toluene 1d 7: 1 86 95 6 toluene 1e 5: 1 82 84

Referring to Table 1, by the selective 1,2-hybrid shift, through the insertion reaction of 1-phenyldiazoethane with the benzaldehyde CH bond under oxazaborolideinium catalyst conditions, 1-11 to 1-6 were synthesized in the same manner as in Example 1, except that the optically active? -Cyclic aryl ketone (2a) was synthesized.

Further, when Examples 1-1 and 1-2 are compared, it can be confirmed that the use of toluene as a non-polar solvent exhibits an increased 2a / 3a ratio, yield and ee as compared with the case of using CH 2 Cl 2 .

Comparing Examples 1-1 to 1-6, the ratio of 2a / 3a, yield and ee when using Catalyst 1d having a 2,4-dimethylphenyl Ar substituent and a 2- (trifluoromethyl) -phenyl R substituent Respectively, which were 7: 1, 86% and 95%, respectively. That is, it can be confirmed that the catalyst 1d exhibits the most excellent activity.

Example 2

In order to confirm the synthesis of the? -Tricaryl ketone of the present invention according to various substituents of the aromatic aldehyde, the reaction was carried out in the same manner as in Examples 2-1 to 2-4 of the present invention, Alpha-tertiary aryl ketone (hereinafter referred to as 2a to 2k) according to 2-11 were synthesized.

[Reaction Scheme 4]

Figure 112015115213575-pat00013

Except that only the catalyst 1d was used as the reaction conditions, the catalysts of Examples 2-4 and 2-6 were carried out at -50 ° C, and the catalysts of Examples 2-5, 2-7, and 2-11 were carried out at -30 ° C. The reaction was carried out under substantially the same reaction conditions as in Example 1. The results are shown in Table 2.

Example 2 2 Ar yield(%) ee (%) One 2a Ph 86 95 2 2b 4-MePh 85 93 3 2c 4-MeOPh 80 95 4 2d 4-BrPh 74 95 5 2e 4-CF 3 Ph 75 95 6 2f 4-CNPh 74 99 7 2g 4-NO 2 Ph 76 94 8 2h 2-FPh 40 96 9 2i 2-thienyl 83 96 10 2j 2-furyl 83 90 11 2k 2-Naph 73 97

Referring to Table 2, it can be seen that Examples 2-8 exhibit relatively low yields due to the unintended Darzen reaction of o -fluorobenzaldehyde, resulting in competitive epoxide formation, resulting in lower (3h) alpha-tertiary aryl ketone (2h) Yield. ≪ / RTI >

However, it can be confirmed that, in various aromatic aldehydes having various Ar substituent groups, the α-tertiary aryl ketone exhibiting high optical activity was synthesized regardless of the characteristics of the respective substituents.

That is, it is confirmed that various α-tertiary aryl ketones having excellent yield and optical activity can be synthesized through the α-tertiary aryl ketone synthesis method of the present invention using various aldehydes.

Example 3

In order to confirm the synthesis of the? -Tricaryl ketone of the present invention according to various aryl diazoalkanes, the reaction was carried out in the same manner as in Examples 3-1 to 3-4 of the present invention, Alpha] -cyclic aryl ketone (hereinafter referred to as 2l to 2r) according to 3-7 was synthesized.

[Reaction Scheme 5]

Figure 112015115213575-pat00014

The reaction conditions were substantially the same as those in Example 1 except that only the catalyst 1d was used and the other aryl diazoalkane was used. The results are shown in Table 3.

Example 3 2 Aryldiazoalkane yield(%) ee (%) One 2l

Figure 112015115213575-pat00015
80 97 2 2m
Figure 112015115213575-pat00016
 88 87 3 2n
Figure 112015115213575-pat00017
 86 86 4 2o
Figure 112015115213575-pat00018
 82 82 5 2p
Figure 112015115213575-pat00019
 78 78 6 2q
Figure 112015115213575-pat00020
 83 83 7 2r
Figure 112015115213575-pat00021
 75 92

Referring to Table 3, it can be seen that the electrical properties of the aryl diazoalkanes affected the yield and the enantioselectivity of the alpha-tertiary aryl ketone.

Specifically, as shown in Example 3-1, electron-rich aryldiazoalkane substrates provided enhanced enantiomeric selectivity, while providing low yields, while Examples 3-2 and 3- As shown in Fig. 3, it can be seen that the electron-deficient substrate causes a slight ee value reduction but provides a-tertiary aryl ketone in high yield.

As shown in Examples 3-4 to 3-7, more stereosubstituted bulky naphthyl and ethyl substituted aryl diazo alkanes, as long as hexyl- and benzyl-, react with benzaldehyde to give high yield and high enantioselectivity -Cyclohexane-1,4-dioxolane.

Example 4

In order to confirm the synthesis of the? -Tricaryl ketone of the present invention according to various substituents of the aliphatic aldehyde and various aryldiazoalkanes, the? -Cycloalkane according to Examples 4-1 to 4-14 of the present invention Aryl ketone (hereinafter referred to as 2s to 2ze) was synthesized.

[Reaction Scheme 6]

Figure 112015115213575-pat00022

 Catalyst 1d was used in Example 4-1, and Catalyst 1e was used in Examples 4-2 to 4-14. In Examples 4-1 to 4-14, aliphatic aldehyde having different substituents was used to react for 2 hours, and substantially the same reaction as in Example 1 was carried out except for Example 4-6, . The results are shown in Table 4.

Example 4 2 Aryldiazoalkane R ' yield(%) ee (%) One 2s

Figure 112015115213575-pat00023
Meat 64 91 2 2s Meat 78 93 3 2t n -hex 83 93 4 2u i- Pr 94 98 5 2v Cyclohexyl 90 99 6 2w t -Bu N.R - 7 2x Meat 72 90 8 2y i- Pr 72 97 9 2z Meat 80 92 10 2za i- Pr 88 96 11 2zb Meat 67 98 12 2zc i- Pr 84 98 13 2zd Meat 55 95 14 2hze i- Pr 68 96

A comparison of Examples 4-1 and 4-2 with reference to Table 4 confirms that the yield of Example 4-2 is better. This indicates that catalyst 1d is the most excellent catalyst in aromatic aldehydes, whereas catalyst 1e is the most excellent catalyst in aliphatic aldehydes. That is, in the case of an aliphatic aldehyde, it can be confirmed that the catalyst 1e supporting o -tolyl group in boron is more suitable for generating a high yield and an enantioselectivity.

In addition, referring to Table 4, as in Examples 4-6, sterically bulky pivaldehyde did not react with 1-phenyldiazoethane at all, while Examples 4-2 to 4- As shown in Fig. 5, isopropyl and cyclohexylcarboxaldehyde, more sterically hindered as well as propionaldehyde, long-chain heptaldehyde, It can be confirmed that it reacts with a zeolite to give an? -Cycloarylketone corresponding to a high yield and excellent electrorheological selectivity.

In general, as described above, by the method of synthesizing an alpha-tertiary aryl ketone according to embodiments of the present invention, the reaction of various aromatic and aliphatic aldehydes with an aryl diazoalkane in the presence of an oxazaborolydidium catalyst, Tertiary aryl ketone corresponding to high yield and excellent electrorheological selectivity can be synthesized.

It will be apparent to those skilled in the art that various modifications and variations can be made in the present invention without departing from the spirit or scope of the present invention as defined by the following claims. It can be understood that it is possible.

Claims (10)

Reacting an aryldiazoalkane represented by the following formula (2) with an aldehyde (Aldehyde) represented by the following formula (3) under a chiral boron Lewis acid catalyst represented by the following formula (1d) or A method for synthesizing an alpha-tertiary aryl ketone, wherein alpha-tertiary aryl ketones are represented by the formula (4);
≪ RTI ID = 0.0 &
Figure 112017057983846-pat00029

[Formula 1e]
Figure 112017057983846-pat00030

(2)
Figure 112017057983846-pat00031

(3)
Figure 112017057983846-pat00032

[Chemical Formula 4]
Figure 112017057983846-pat00033

In the above Chemical Formulas 2 to 4, Ar 1 represents an aryl group, R 1 represents an alkyl group, Ar 2 represents an aryl group or an alkyl group,
When Ar 2 is an aryl group,
The chiral boron Lewis acid catalyst is a compound represented by the above formula (1d)
When Ar 2 is an alkyl group,
Wherein the chiral boron Lewis acid catalyst is the compound represented by the formula (1e)
A method for synthesizing? -criminal aryl ketone.
delete The method according to claim 1,
Characterized in that the chiral boron Lewis acid catalyst is activated by triflic acid.
A method for synthesizing? -criminal aryl ketone.
The method according to claim 1,
Characterized in that the chiral boron Lewis acid catalyst is used in a concentration of 20 mol%
A method for synthesizing? -criminal aryl ketone.
delete delete delete delete The method according to claim 1,
0.30 mmol to 0.40 mmol of the aryl diazoalkane and 0.20 mmol to 0.30 mmol of the aldehyde are reacted,
A method for synthesizing? -criminal aryl ketone.
10. The method of claim 9,
Wherein the aryldiazoalkane and the aldehyde are reacted at -85 DEG C to 0 DEG C for 20 minutes to 130 minutes.
A method for synthesizing? -criminal aryl ketone.
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