Method for producing alkyl-substituted polycyclic aromatic compound

Abstract

To provide a method for position-selective alkylation of a polycyclic aromatic compound.SOLUTION: A production method comprises a step of reacting a polycyclic aromatic compound with a compound represented by the formula (2A) or (2B) in the figure under irradiation with ultraviolet light or visible light.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a method for producing an alkyl-substituted polycyclic aromatic compound. [Background technology]

[0002] Methods for producing aromatic compounds are particularly important in organic chemistry. Modern aromatic substructures are found in virtually all pharmaceutical compounds and are key components of many polymers and materials. Among aromatic compounds, polycyclic aromatic hydrocarbons (PAHs) have attracted much attention, both as fragments of graphene and as interesting materials in their own right. Functionalized PAHs have already shown promise in a variety of applications, including organic electronic devices, bioimaging, sensing, and gene delivery. In recent years, several bottom-up approaches have been developed that enable the preparation of atomically precise new PAHs, including systems containing heteroatoms and rings of various sizes. To explore the functionality of these new PAHs, methods for modifying edge sites are crucial. These methods improve PAH solubility and processability and allow for tuning of intermolecular interactions and electronic properties, all of which are important factors in materials applications. However, the construction of polycyclic aromatic hydrocarbons (PAHs) often requires harsh reaction conditions, limits the applicable functional groups, and requires several steps to prepare suitable precursors for the regioselective introduction of desired substituents. Therefore, the development of a simple method for regioselectively functionalizing the carbon-hydrogen (C-H) bonds of polycyclic aromatic hydrocarbons (PAHs) is essential.

[0003] Among the direct methods for introducing functional groups into polycyclic aromatic hydrocarbons (PAHs), the Friedel-Crafts alkylation reaction is the most widely used (see, for example, Non-Patent Document 1). As expected from this classic reaction, the Friedel-Crafts alkylation reaction requires a strong acid (see, for example, Non-Patent Documents 2-3). As a result, the compatibility of functional groups is low, and the groups that can be introduced are limited to very simple alkyl groups. Precise control of regioselectivity is also an important challenge when employing the Friedel-Crafts reaction on polycyclic aromatic hydrocarbons (PAHs). For example, when the PAH is pyrene, electrophilic aromatic substitution generally occurs at the C1, C3, C6, and C8 positions, while bulky tertiary alkyl groups are substituted at the C2 and C7 positions. To date, there has been one example of tertiary alkylation of pyrene at the C1 position under electrochemical conditions, making selective synthesis difficult because hydrogenated pyrenes also result. Therefore, the regioselectivity in classical thermal functionalization of polycyclic aromatic hydrocarbons (PAHs) depends on the bulkiness of the substituents, greatly complicating the synthetic efforts to prepare structurally diverse polycyclic aromatic hydrocarbon (PAH) derivatives. [Prior art documents] [Non-patent literature]

[0004] [Non-Patent Document 1] PH Gore, The Friedel-Crafts Acylation Reaction and its Application to Polycyclic Aromatic Hydrocarbons, Chem. Rev. 55, 229-281 (1955). [Non-patent document 2] L. Rodenburg, R. Brandsma, C. Tintel, J. van Thujil, J. Lugtenburg, J. Cornelisse, Synthesis and Properties of Nitro Derivatives of 2-tert-Butyl- and 2,7-Di-tert-butylpyrene. Recl. Trav. Chim. Pays-Bas 105, 156-161 (1986). [Non-patent document 3] A. Wrona-Piotrowicz, A. Makal, J. Zakrzewski, Triflic Acid-Promoted Adamantylation and tert-Butylation of Pyrene: Fluorescent Properties of Pyrene-Decorated Adamantanes and a Channeled Crystal Structure of 1,3,5-Tris(pyren-2-yl)adamantane. J. Org. Chem. 85, 11134-11139 (2020). Summary of the Invention [Problem to be solved by the invention]

[0005] The present invention has been made in view of the above-mentioned problems, and an object of the present invention is to provide a method capable of regioselectively alkylating polycyclic aromatic compounds. [Means for solving the problem]

[0006] The present inventors have conducted extensive research to solve the above-mentioned problems. As a result, they have found that by reacting a specific polycyclic aromatic compound with a sulfone compound or the like having a tetrazole skeleton under irradiation with ultraviolet or visible light, even a bulky alkyl group can be regioselectively alkylated with the specific polycyclic aromatic compound. Based on this finding, the present inventors have conducted further extensive research and completed the present invention. The present invention encompasses the following features.

[0007] Term 1. General formula (1):

[0008] [ka] [In the formula, Ar 1 R represents a fused aromatic ring having 4 to 6 rings (excluding chrysene ring, triphenylene ring, and dibenzo[g,p]chrysene ring), a thienothiophene ring, a benzo[f]indole ring, a benzodithiophene ring, a benzodifuran ring, or a naphthothiophene ring. 1 represents an alkyl group, and n represents an integer of 1 to 4.] A method for producing a compound represented by the formula: The Ar 1 a polycyclic aromatic compound consisting of General formula (2A) or (2B):

[0009] [ka] [In the formula, R 1 is the same as above. R 2 represents an alkyl group or an aryl group. 3 represents a halogen atom, an alkyl group, or an alkoxy group, and m represents an integer of 0 to 4. and a compound represented by A step of reacting under ultraviolet or visible light irradiation A manufacturing method comprising:

[0010] Section 2. Said R 1 Item 1. The method for producing according to Item 1, wherein is a tertiary alkyl group.

[0011] Item 3. Said Ar 1 is a pyrene ring, a fluoranthene ring, a perylene ring, a thienothiophene ring, a benzo[f]indole ring, a benzodithiophene ring, a benzodifuran ring, or a naphthothiophene ring.

[0012] Item 4. The production method according to any one of Items 1 to 3, wherein the reaction is carried out in the presence of a metal compound and / or an ammonium salt.

[0013] Item 5. The production method according to Item 4, wherein the metal constituting the metal compound is at least one metal selected from the group consisting of alkali metals, alkaline earth metals, and zinc.

[0014] Item 6. The production method according to any one of Items 1 to 5, wherein the reaction is carried out in the presence of a base.

[0015] Item 7. The production method according to Item 6, wherein the base is at least one selected from the group consisting of carbonates, phosphates, acetates, hydroxides, alkoxides, and amines.

[0016] Item 8. The production method according to any one of Items 1 to 7, wherein the reaction is carried out in the presence of an organic solvent.

[0017] Item 9. The production method according to Item 8, wherein the organic solvent is an amide solvent and / or a sulfoxide solvent.

[0018] Item 10. The method according to any one of Items 1 to 9, wherein the ultraviolet light or visible light is emitted from a light source having a peak wavelength of 300 to 800 nm.

[0019] Section 11. General formulas (1A1)~(1A5):

[0020] [ka] [In the formula, R 1a , R 1e , R 1g , R1k and R 1m are the same or different and represent an alkyl group. 1b , R 1c , R 1d , R 1f , R 1h , R 1i , R 1j and R 1l R may be the same or different and represent a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, an aryl group, a heterocyclic group, an amino group, an alkylcarbonyl group, an alkoxycarbonyl group, an aminocarbonyl group, a silyl group, or a boronic acid or ester group thereof. 2a , R 2b , R 2c , R 2d , R 2e and R 2f are the same or different and represent a halogen atom, an alkyl group, an alkoxy group, an aryl group, a heterocyclic group, an amino group, an alkylcarbonyl group, an alkoxycarbonyl group, an aminocarbonyl group, a silyl group, or a boronic acid or ester group thereof. m1 is an integer of 0 to 6. m2 and m3 are the same or different and represent an integer of 0 to 8. m4 is an integer of 0 to 2. m5 is an integer of 0 to 7. A compound represented by any of the following:

[0021] Section 12. General formula (2A1):

[0022] [ka] [In the formula, R 1 represents an alkyl group. 2a represents an alkyl group substituted with an aryl group or an aryl group substituted with an alkyl group.] A compound represented by the formula: [Effects of the Invention]

[0023] According to the present invention, polycyclic aromatic compounds can be alkylated regioselectively. [Brief explanation of the drawings]

[0024] [Figure 1] 1 shows the results of the on / off test of Example 4. DETAILED DESCRIPTION OF THE INVENTION

[0025] In this specification, the term "containing" is a concept that encompasses all of "comprise," "consist essentially of," and "consist only of."

[0026] In addition, in this specification, when a numerical range is expressed as "A to B," it means A or more and B or less.

[0027] The production method of the present invention comprises reacting a compound represented by general formula (1):

[0028] [ka] [In the formula, Ar 1 R represents a fused aromatic ring having 4 to 6 rings (excluding chrysene ring, triphenylene ring, and dibenzo[g,p]chrysene ring), a thienothiophene ring, a benzo[f]indole ring, a benzodithiophene ring, a benzodifuran ring, or a naphthothiophene ring. 1 represents an alkyl group, and n represents an integer of 1 to 4.] A method for producing a compound represented by the formula: The Ar 1 a polycyclic aromatic compound consisting of General formula (2A) or (2B):

[0029] [ka] [In the formula, R 1 is the same as above. R 2 represents an alkyl group or an aryl group. 3 represents a halogen atom, an alkyl group, or an alkoxy group. m represents an integer of 0 to 4.] and a compound represented by A step of reacting under ultraviolet or visible light irradiation Equipped with.

[0030] 1. Polycyclic aromatic compounds (substrates) and alkyl-substituted polycyclic aromatic compounds (target products) In the general formula (1), Ar 1 means a fused aromatic ring constituting the substrate polycyclic aromatic compound, and refers to a fused aromatic ring having 4 to 6 rings (excluding chrysene ring, triphenylene ring, and dibenzo[g,p]chrysene ring), a thienothiophene ring, or a benzo[f]indole ring. Specific examples include a pyrene ring, a fluoranthene ring, a perylene ring, a thienothiophene ring, a benzo[f]indole ring, a benzodithiophene ring, a benzodifuran ring, and a naphthothiophene ring.

[0031] These fused aromatic rings may also have substituents. 1 The substituent that may be possessed by is not particularly limited, but examples thereof include a halogen atom, an alkyl group, an alkoxy group, an aryl group, a heterocyclic group, an amino group, an alkylcarbonyl group, an alkoxycarbonyl group, an aminocarbonyl group, a silyl group, or a boronic acid or ester group thereof.

[0032] These substituents are explained below.

[0033] The halogen atom is not particularly limited, and examples thereof include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

[0034] The alkyl group is not particularly limited, and any of a linear alkyl group, a branched alkyl group, and a cyclic alkyl group (cycloalkyl group) can be used. Preferred are linear alkyl groups having 1 to 20 carbon atoms (particularly 1 to 10), branched alkyl groups having 3 to 20 carbon atoms (particularly 3 to 10), and cyclic alkyl groups (cycloalkyl groups) having 3 to 20 carbon atoms (particularly 4 to 18), and examples thereof include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and an androsteronyl group.

[0035] These alkyl groups may also have a substituent. Examples of the substituent that the alkyl group may have include an oxygen atom, a hydroxyl group, the halogen atoms described above, the alkyl groups described above, the alkoxy groups described below, the aryl groups described below, the heterocyclic groups described below, the amino groups described below, the alkylcarbonyl groups described below, the alkoxycarbonyl groups described below, the aminocarbonyl groups described below, the silyl groups described below, the boronic acid or ester groups thereof described below, acyloxy groups (acetyloxy groups, propionyloxy groups, butyryloxy groups, etc.; including those substituted with the alkoxycarbonyl groups described below), siloxy groups (siloxy groups, trimethylsiloxy groups, tert-butyldimethylsiloxy groups, triethylsiloxy groups, etc.), phosphoryl groups (dimethoxyphosphoryl groups, diethoxyphosphoryl groups, etc.), and cyano groups. When the alkyl group has a substituent, the number of substituents can be, for example, 1 to 6, and particularly 1 to 3.

[0036] The alkoxy group is not particularly limited, and any of a linear alkoxy group, a branched alkoxy group, and a cyclic alkoxy group (cycloalkoxy group) can be used. Preferred are linear alkoxy groups having 1 to 20 carbon atoms (particularly 1 to 10), branched alkoxy groups having 3 to 20 carbon atoms (particularly 3 to 10), and cyclic alkoxy groups (cycloalkoxy groups) having 3 to 20 carbon atoms (particularly 4 to 18), and examples thereof include a methoxy group, an ethoxy group, an n-propyloxy group, an isopropyloxy group, an n-butyloxy group, an isobutyloxy group, a sec-butyloxy group, a tert-butyloxy group, a cyclopropyloxy group, a cyclobutyloxy group, a cyclopentyloxy group, a cyclohexyloxy group, and a cycloheptyloxy group.

[0037] These alkoxy groups may have a substituent. Examples of the substituent that the alkoxy group may have include an oxygen atom, a hydroxyl group, the halogen atom, the alkyl group, the alkoxy group, the aryl group described below, the heterocyclic group described below, the amino group described below, the alkylcarbonyl group described below, the alkoxycarbonyl group described below, the aminocarbonyl group described below, the silyl group described below, the boronic acid or its ester group described below, an acyloxy group (such as an acetyloxy group, a propionyloxy group, a butyryloxy group; including those substituted with the alkoxycarbonyl group described below), a siloxy group (such as a siloxy group, a trimethylsiloxy group, a tert-butyldimethylsiloxy group, a triethylsiloxy group), a phosphoryl group (such as a dimethoxyphosphoryl group or a diethoxyphosphoryl group), and a cyano group. When the alkoxy group has a substituent, the number of substituents can be, for example, 1 to 6, and particularly 1 to 3.

[0038] The aryl group is not particularly limited and may be either monocyclic or polycyclic (for example, bicyclic, tricyclic, etc.) Specific examples of the aryl group include a phenyl group, a naphthyl group, a biphenyl group, a pentalenyl group, an indanyl group, an anthranyl group, a tetracenyl group, a pentacenyl group, a pyrenyl group, a perylenyl group, a fluorenyl group, and a phenanthryl group.

[0039] These aryl groups may have a substituent. Examples of the substituent that the aryl group may have include an oxygen atom, a hydroxyl group, the halogen atoms, the alkyl groups, the alkoxy groups, the aryl groups, the heterocyclic groups described below, the amino groups described below, the alkylcarbonyl groups described below, the alkoxycarbonyl groups described below, the aminocarbonyl groups described below, the silyl groups described below, the boronic acids or ester groups thereof described below, acyloxy groups (acetyloxy groups, propionyloxy groups, butyryloxy groups, etc.; including those substituted with the alkoxycarbonyl groups described below), siloxy groups (siloxy groups, trimethylsiloxy groups, tert-butyldimethylsiloxy groups, triethylsiloxy groups, etc.), phosphoryl groups (dimethoxyphosphoryl groups, diethoxyphosphoryl groups, etc.), and cyano groups. When the aryl group has a substituent, the number of substituents can be, for example, 1 to 6, and particularly 1 to 3.

[0040] The heterocyclic group is not particularly limited, and examples of the heterocyclic group include a nitrogen-containing heterocyclic group, an oxygen-containing heterocyclic group, a sulfur-containing heterocyclic group, and a silicon-containing heterocyclic group. Specific examples of the heterocyclic group include a pyrrolyl group, a furanyl group, a thienyl group, a silacyclopentadienyl group, an imidazolyl group, an imidazolinyl group, a pyrazolyl group, an oxazolyl group, a thiazolyl group, a triazolyl group, an oxadiazolyl group, a thiadiazolyl group, a tetrazolyl group, a pyridyl group, a pyridazyl group, a pyrimidyl group, a pyrazyl group, an indolyl group, an isoindolyl group, a benzimidazolyl group, and a benzotriazolyl group. aromatic heterocyclic groups such as a quinolyl group, an isoquinolyl group, a quinazolyl group, a quinoxalyl group, a carbazolyl group, a benzodithienyl group, a benzodifuranyl group, and a naphthothienyl group; and aliphatic heterocyclic groups such as a pyrrolidinyl group, a tetrahydrofuranyl group, a tetrahydrothienyl group, a dioxolanyl group, a piperidinyl group, a tetrahydropyranyl group, a tetrahydrothiopyranyl group, a dioxanyl group, and a morpholinyl group.

[0041] These heterocyclic groups may also have a substituent. Examples of the substituent that the heterocyclic group may have include an oxygen atom, a hydroxyl group, the halogen atoms, the alkyl groups, the alkoxy groups, the aryl groups, the heterocyclic groups, the amino groups described below, the alkylcarbonyl groups described below, the alkoxycarbonyl groups described below, the aminocarbonyl groups described below, the silyl groups described below, the boronic acids or ester groups thereof described below, acyloxy groups (acetyloxy groups, propionyloxy groups, butyryloxy groups, etc.; including those substituted with the alkoxycarbonyl groups described below), siloxy groups (siloxy groups, trimethylsiloxy groups, tert-butyldimethylsiloxy groups, triethylsiloxy groups, etc.), phosphoryl groups (dimethoxyphosphoryl groups, diethoxyphosphoryl groups, etc.), and cyano groups. When the heterocyclic group has a substituent, the number of substituents can be, for example, 1 to 6, and particularly 1 to 3.

[0042] The amino group may have a substituent. Examples of the substituent that the amino group may have include an oxygen atom, a hydroxyl group, the halogen atoms, the alkyl groups, the alkoxy groups, the aryl groups, the heterocyclic groups, the amino groups, the alkylcarbonyl groups described below, the alkoxycarbonyl groups described below, the aminocarbonyl groups described below, the silyl groups described below, the boronic acids or ester groups thereof described below, acyloxy groups (acetyloxy groups, propionyloxy groups, butyryloxy groups, etc.; including those substituted with the alkoxycarbonyl groups described below), siloxy groups (siloxy groups, trimethylsiloxy groups, tert-butyldimethylsiloxy groups, triethylsiloxy groups, etc.), phosphoryl groups (dimethoxyphosphoryl groups, diethoxyphosphoryl groups, etc.), and cyano groups. When the amino group has a substituent, the number of substituents can be, for example, 1 to 3, and particularly 1 to 2.

[0043] The alkylcarbonyl group may have an alkylcarbonyl group having the above alkyl group, and specific examples thereof include a methylcarbonyl group and an ethylcarbonyl group.

[0044] These alkylcarbonyl groups may also have a substituent. Examples of the substituent that the alkylcarbonyl group may have include an oxygen atom, a hydroxyl group, the halogen atoms, the alkyl groups, the alkoxy groups, the aryl groups, the heterocyclic groups, the amino groups, the alkylcarbonyl groups, the alkoxycarbonyl groups described below, the aminocarbonyl groups described below, the silyl groups described below, the boronic acids or ester groups thereof described below, acyloxy groups (acetyloxy groups, propionyloxy groups, butyryloxy groups, etc.; including those substituted with the alkoxycarbonyl groups described below), siloxy groups (siloxy groups, trimethylsiloxy groups, tert-butyldimethylsiloxy groups, triethylsiloxy groups, etc.), phosphoryl groups (dimethoxyphosphoryl groups, diethoxyphosphoryl groups, etc.), and cyano groups. When the alkylcarbonyl group has a substituent, the number of substituents can be, for example, 1 to 6, and particularly 1 to 3.

[0045] The alkoxycarbonyl group can have an alkoxycarbonyl group having the above-mentioned alkoxy group, and specific examples thereof include a methoxycarbonyl group, an ethoxycarbonyl group, a propyloxycarbonyl group (n-propyloxycarbonyl group, isopropyloxycarbonyl group), a butyloxycarbonyl group (n-butyloxycarbonyl group, isobutyloxycarbonyl group, sec-butyloxycarbonyl group, tert-butyloxycarbonyl group, etc.), and the like.

[0046] These alkoxycarbonyl groups can also have a substituent.The substituent that the alkoxycarbonyl group may have includes, for example, an oxygen atom, a hydroxyl group, the above-mentioned halogen atom, the above-mentioned alkyl group, the above-mentioned alkoxy group, the above-mentioned aryl group, the above-mentioned heterocyclic group, the above-mentioned amino group, the above-mentioned alkylcarbonyl group, the above-mentioned alkoxycarbonyl group, the aminocarbonyl group described below, the silyl group described below, the boronic acid or its ester group described below, an acyloxy group (acetyloxy group, propionyloxy group, butyryloxy group, etc.; including those substituted with the above-mentioned alkoxycarbonyl group, etc.), a siloxy group (siloxy group, trimethylsiloxy group, tert-butyldimethylsiloxy group, triethylsiloxy group, etc.), a phosphoryl group (dimethoxyphosphoryl group, diethoxyphosphoryl group, etc.), a cyano group, etc., and the alkoxycarbonyl group having these substituents also includes a benzyloxycarbonyl group (Cbz) and the like. When the alkoxycarbonyl group has a substituent, the number of the substituents can be, for example, 1 to 6, and particularly 1 to 3.

[0047] The aminocarbonyl group may have an aminocarbonyl group having the above amino group, and specific examples thereof include an aminocarbonyl group, a dimethylaminocarbonyl group, and a diethylaminocarbonyl group.

[0048] These aminocarbonyl groups may also have a substituent. Examples of the substituent that the aminocarbonyl group may have include an oxygen atom, a hydroxyl group, the halogen atoms, the alkyl groups, the alkoxy groups, the aryl groups, the heterocyclic groups, the amino groups, the alkylcarbonyl groups, the alkoxycarbonyl groups, the aminocarbonyl groups, the silyl groups described below, the boronic acids or ester groups thereof described below, acyloxy groups (acetyloxy groups, propionyloxy groups, butyryloxy groups, etc.; including those substituted with the alkoxycarbonyl groups, etc.), siloxy groups (siloxy groups, trimethylsiloxy groups, tert-butyldimethylsiloxy groups, triethylsiloxy groups, etc.), phosphoryl groups (dimethoxyphosphoryl groups, diethoxyphosphoryl groups, etc.), and cyano groups. When the aminocarbonyl group has a substituent, the number of substituents can be, for example, 1 to 6, and particularly 1 to 3.

[0049] The silyl group is not particularly limited, and in addition to an unsubstituted silyl group, a trialkylsilyl group (a silyl group having the above-mentioned alkyl group) can be used. Examples include a silyl group, a trimethylsilyl group (TMS), and a triethylsilyl group.

[0050] These silyl groups may have a substituent. Examples of the substituent that the silyl group may have include an oxygen atom, a hydroxyl group, the halogen atoms, the alkyl groups, the alkoxy groups, the aryl groups, the heterocyclic groups, the amino groups, the alkylcarbonyl groups, the alkoxycarbonyl groups, the aminocarbonyl groups, the silyl groups, the boronic acid or ester groups thereof described below, acyloxy groups (acetyloxy groups, propionyloxy groups, butyryloxy groups, etc.; including those substituted with the alkoxycarbonyl groups, etc.), siloxy groups (siloxy groups, trimethylsiloxy groups, tert-butyldimethylsiloxy groups, triethylsiloxy groups, etc.), phosphoryl groups (dimethoxyphosphoryl groups, diethoxyphosphoryl groups, etc.), and cyano groups. When the silyl group has a substituent, the number of substituents can be, for example, 1 to 6, and particularly 1 to 3.

[0051] The boronic acid or ester group thereof is

[0052] [ka] [In the formula, R 3a and R 3b are the same or different and represent a hydrogen atom or an alkyl group. 3a and R 3b may be taken together with the adjacent -OBO- to form a ring. A group represented by the following formula is preferred.

[0053] R of the above boronic acid or its ester group 3a and R 3b is a hydrogen atom or the above alkyl group.

[0054] Also, R 3a and R 3b When is an alkyl group, R 3a and R 3b may combine with the adjacent -OBO- to form a ring. In this case, the two oxygen atoms are bonded via an alkylene group (an alkylene group having 1 to 10 carbon atoms, such as a methylene group, an ethylene group, a trimethylene group, or a tetramethylene group).

[0055] Examples of such boronic acid or ester groups include:

[0056] [ka] [In the formula, R 4a , R 4b , R 4c , R 4d , R 4e and R 4f are the same or different and represent a hydrogen atom or an alkyl group. Examples of the group include a group represented by the following formula:

[0057] The above R 4a , R 4b , R 4c, R 4d , R 4e and R 4f is a hydrogen atom or the above alkyl group.

[0058] These boronic acids or their ester groups may also have a substituent. Examples of the substituent that the boronic acid or its ester group may have include an oxygen atom, a hydroxyl group, the halogen atoms, the alkyl groups, the alkoxy groups, the aryl groups, the heterocyclic groups, the amino groups, the alkylcarbonyl groups, the alkoxycarbonyl groups, the aminocarbonyl groups, the silyl groups, the boronic acids or their ester groups, acyloxy groups (acetyloxy groups, propionyloxy groups, butyryloxy groups, etc.; including those substituted with the alkoxycarbonyl groups), siloxy groups (siloxy groups, trimethylsiloxy groups, tert-butyldimethylsiloxy groups, triethylsiloxy groups, etc.), phosphoryl groups (dimethoxyphosphoryl groups, diethoxyphosphoryl groups, etc.), and cyano groups. When the boronic acid or its ester group has a substituent, the number of substituents may be, for example, 1 to 6, and particularly 1 to 3.

[0059] Ar that meets the above conditions 1 is a pyrene ring which may have a substituent, a fluoranthene ring which may have a substituent, a perylene ring which may have a substituent, a thienothiophene ring which may have a substituent, a benzo[f]indole ring which may have a substituent, or the like, the polycyclic aromatic compound which is the substrate is, for example, a compound represented by the general formulas (3A1) to (3A5):

[0060] [ka] [In the formula, R 3b , R 3c , R 3d , R 3f , R 3h , R 3i , R 3j and R 3lR may be the same or different and represent a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, an aryl group, a heterocyclic group, an amino group, an alkylcarbonyl group, an alkoxycarbonyl group, an aminocarbonyl group, a silyl group, or a boronic acid or ester group thereof. 2a , R 2b , R 2c , R 2d , R 2e and R 2f are the same or different and represent a halogen atom, an alkyl group, an alkoxy group, an aryl group, a heterocyclic group, an amino group, an alkylcarbonyl group, an alkoxycarbonyl group, a silyl group, or a boronic acid or ester group thereof. m1 is an integer of 0 to 6. m2 and m3 are the same or different and represent an integer of 0 to 8. m4 is an integer of 0 to 2. m5 is an integer of 0 to 7. * indicates that R 1 means the position where an alkyl group represented by the following formula is introduced.] It can be expressed as:

[0061] Also, R 3b , R 3c , R 3d , R 3f , R 3h , R 3i , R 3j and R 3l means a group originally possessed by the substrate polycyclic aromatic compound. 3b , R 3c , R 3d , R 3f , R 3h , R 3i , R 3j and R 3l are hydrogen atoms, R 1 An alkyl group represented by the following formula can also be introduced.

[0062] Also, R 2a , R 2b , R 2c , R 2d , R 2e and R 2f means a group that the substrate polycyclic aromatic compound originally has.

[0063] In the general formulae (3A1) to (3A5), the halogen atom, alkyl group, alkoxy group, aryl group, heterocyclic group, amino group, alkylcarbonyl group, alkoxycarbonyl group, silyl group, boronic acid or its ester group, etc. may be those described above.

[0064] In addition, in the general formula (3A1), R 2a m1, which means the number of, is an integer of 0 to 6, preferably an integer of 0 to 3, and more preferably an integer of 0 to 2.

[0065] In addition, in the general formulae (3A2) to (3A3), R 2b and R 2c m2 and m3, which represent the number of the aryl groups, are integers of 0 to 8, preferably integers of 0 to 4, and more preferably integers of 0 to 2.

[0066] In addition, in general formula (3A4), R 2d m4, which means the number of, is an integer of 0 to 2, and 0 or 1 is preferred.

[0067] In addition, in general formula (3A5), R 2e m5, which means the number of, is an integer of 0 to 7, preferably an integer of 0 to 4, and more preferably an integer of 0 to 2.

[0068] Specific examples of polycyclic aromatic compounds that are substrates that satisfy these conditions include:

[0069] [ka] However, not all polycyclic aromatic compounds can cause the reaction of the present invention; the compound must be a fused aromatic ring having 4 to 6 rings (excluding chrysene rings, triphenylene rings, and dibenzo[g,p]chrysene rings), a thienothiophene ring, a benzo[f]indole ring, a benzodithiophene ring, a benzodifuran ring, or a naphthothiophene ring.

[0070] In general formula (1), R 1 means an alkyl group introduced by a polycyclic aromatic compound by the production method of the present invention. This alkyl group can be any of a primary alkyl group, a secondary alkyl group, a tertiary alkyl group, and a cyclic alkyl group (cycloalkyl group), and is preferably a primary alkyl group having 1 to 20 carbon atoms (particularly 1 to 10), a secondary alkyl group having 3 to 20 carbon atoms (particularly 3 to 10), a tertiary alkyl group having 3 to 20 carbon atoms (particularly 3 to 10), or a cyclic alkyl group (cycloalkyl group) having 3 to 20 carbon atoms (particularly 4 to 18), etc., and examples thereof include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, an androsteronyl group, etc.

[0071] These alkyl groups can also have a substituent. Examples of the substituent that the alkyl group may have include an oxygen atom, a hydroxyl group, the halogen atom, the alkyl group, the aryl group described below, the heterocyclic group described below, the alkylcarbonyl group described below, the alkoxycarbonyl group described below, the silyl group described below, the boronic acid or its ester group described below, an alkoxy group (an alkoxy group having the alkyl group described above, such as a methoxy group or an ethoxy group), an aminocarbonyl group (a dimethylaminocarbonyl group, a diethylaminocarbonyl group, etc.), an acyloxy group (an acetyloxy group, a propionyloxy group, a butyryloxy group, etc.; including those substituted with the alkoxycarbonyl group described below), a siloxy group (a siloxy group, a trimethylsiloxy group, a tert-butyldimethylsiloxy group, a triethylsiloxy group, etc.), a phosphoryl group (a dimethoxyphosphoryl group, a diethoxyphosphoryl group, etc.), a cyano group, etc. When the alkyl group has a substituent, the number of the substituents can be, for example, 1 to 6, and particularly 1 to 3.

[0072] Among these, the present invention is particularly useful when introducing a bulky alkyl group, from the viewpoint that even a bulky alkyl group can be alkylated regioselectively. 1The alkyl group represented by the formula (I) is preferably a secondary alkyl group, a tertiary alkyl group, or a cyclic alkyl group (cycloalkyl group), more preferably a tertiary alkyl group or a cyclic alkyl group (cycloalkyl group), and particularly preferably a tertiary alkyl group.

[0073] R as above 1 One or two of may be introduced into the polycyclic aromatic compound. Therefore, in general formula (1), n is an integer of 1 to 4, preferably an integer of 1 to 3, and more preferably 1 or 2.

[0074] Ar that meets the above conditions 1 is an optionally substituted pyrene ring, an optionally substituted fluoranthene ring, an optionally substituted perylene ring, an optionally substituted thienothiophene ring, an optionally substituted benzo[f]indole ring, or the like, the target alkyl-substituted polycyclic aromatic compound can be represented, for example, by the general formulas (1A1) to (1A5):

[0075] [ka] [In the formula, R 1a , R 1e , R 1g , R 1k and R 1m are the same or different and represent an alkyl group. 1b , R 1c , R 1d , R 1f , R 1h , R 1i , R 1j and R 1l R may be the same or different and represent a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, an aryl group, a heterocyclic group, an amino group, an alkylcarbonyl group, an alkoxycarbonyl group, an aminocarbonyl group, a silyl group, or a boronic acid or ester group thereof. 2a , R 2b , R 2c , R 2d , R 2e and R 2fare the same or different and represent a halogen atom, an alkyl group, an alkoxy group, an aryl group, a heterocyclic group, an amino group, an alkylcarbonyl group, an alkoxycarbonyl group, an aminocarbonyl group, a silyl group, or a boronic acid or ester group thereof. m1 is an integer of 0 to 6. m2 and m3 are the same or different and represent an integer of 0 to 8. m4 is an integer of 0 to 2. m5 is an integer of 0 to 7. It can be expressed as:

[0076] where R 1a , R 1e , R 1g , R 1k and R 1m is R in general formula (1) 1 and means the alkyl group introduced by the production method of the present invention.

[0077] Also, R 1b , R 1c , R 1d , R 1f , R 1h , R 1i , R 1j and R 1l In other cases, R also includes an alkyl group. Therefore, when two alkyl groups are introduced by the production method of the present invention, alkyl groups can also be introduced at these positions by the production method of the present invention. 1b , R 1c , R 1d , R 1f , R 1h , R 1i , R 1j and R 1l means a group that the substrate polycyclic aromatic compound originally has.

[0078] Also, R 2a , R 2b , R 2c , R 2d , R 2e and R 2f means a group that the substrate polycyclic aromatic compound originally has.

[0079] In the general formulae (1A1) to (1A5), the halogen atom, alkyl group, alkoxy group, aryl group, heterocyclic group, amino group, alkylcarbonyl group, alkoxycarbonyl group, aminocarbonyl group, silyl group, boronic acid or its ester group, etc. may be those described above.

[0080] In addition, in the general formula (1A1), R 2a m1, which means the number of, is an integer of 0 to 6, preferably an integer of 0 to 3, and more preferably an integer of 0 to 2.

[0081] In addition, in the general formulae (1A2) to (1A3), R 2b and R 2c m2 and m3, which represent the number of the aryl groups, are integers of 0 to 8, preferably integers of 0 to 4, and more preferably integers of 0 to 2.

[0082] In addition, in general formula (1A4), R 2d m4, which means the number of, is an integer of 0 to 2, and 0 or 1 is preferred.

[0083] In addition, in general formula (1A5), R 2e m5, which means the number of, is an integer of 0 to 7, preferably an integer of 0 to 4, and more preferably an integer of 0 to 2.

[0084] These compounds represented by general formulae (1A1) to (1A5) are novel compounds that have not been described in the literature.

[0085] Specific examples of alkyl-substituted polycyclic aromatic compounds that satisfy these conditions include:

[0086] [ka]

[0087] [ka]

[0088] [ka]

[0089] [ka]

[0090] [ka]

[0091] [ka] [In the formula, Cbz represents a benzyloxycarbonyl group, and Boc represents a tert-butyloxycarbonyl group.] etc.

[0092] 2. Compounds represented by general formula (2A) or (2B) (reactants) In the production method of the present invention, the polycyclic aromatic compound as the substrate is reacted with a specific compound, thereby enabling regioselective alkylation of the polycyclic aromatic compound.

[0093] The compound usable as the reactant in this case is represented by the general formula (2A) or (2B):

[0094] [ka] [In the formula, R 1 is the same as above. R 2 represents an alkyl group or an aryl group. 3 represents a halogen atom, an alkyl group, or an alkoxy group. m represents an integer of 0 to 4.] In general formula (2A) and (2B), R 1 means an alkyl group introduced into the polycyclic aromatic compound.

[0095] In general formulas (2A) and (2B), R 2alkyl and aryl groups represented by the formula: R 3 As the halogen atom, alkyl group and alkoxy group represented by the formula (I), those mentioned above can be used.

[0096] In addition, in the general formula (2B), R 3 m, which means the number of, is an integer of 0 to 4, preferably an integer of 0 to 2, and more preferably 0 or 1.

[0097] Specific examples of the compounds represented by general formulas (2A) and (2B) that satisfy these conditions include:

[0098] [ka]

[0099] [ka]

[0100] [ka] [In the formula, Cbz represents a benzyloxycarbonyl group, and Boc represents a tert-butyloxycarbonyl group.] etc.

[0101] The compounds represented by the general formula (2A) or (2B) as the reactants can be used alone or in combination of two or more kinds.

[0102] The amount of the compound represented by general formula (2A) or (2B) used as a reactant is not particularly limited, but is preferably 1.5 to 10.0 mol, more preferably 2.0 to 7.0 mol, per mol of the polycyclic aromatic compound substrate, from the viewpoints of reaction conversion rate, selectivity for the target product, yield, etc. When multiple compounds represented by general formula (2A) or (2B) are used as reactants, it is preferable to adjust the total amount thereof to be within the above range.

[0103] Among these compounds represented by the general formula (2A) or (2B) as reactants, the compound represented by the general formula (2A1):

[0104] [ka] [In the formula, R 1 represents an alkyl group. 2a represents an alkyl group substituted with an aryl group or an aryl group substituted with an alkyl group.] The compound represented by the formula (I) is a novel compound that has not been described in any literature.

[0105] In general formula (2A1), R 1 and R 3 The alkyl group shown, R 2 As the alkyl group and aryl group in the formula (I), those mentioned above can be used.

[0106] The compounds represented by the general formula (2A) or (2B) as the reactants are, for example, compounds represented by the general formula (4):

[0107] [ka] [In the formula, R 2a is the same as above.] and a compound represented by general formula (5A): R 1 -X (5A) [In the formula, R 1 is the same as above. X represents the above halogen atom.] (0.5 to 3.0 mol, particularly 1.0 to 2.0 mol relative to 1 mol of the compound represented by general formula (4)) in an organic solvent (tetrahydrofuran (THF) or the like) in the presence of a base (potassium carbonate, diazabicycloundecene (DBU) or the like; 0.5 to 3.0 mol, particularly 1.0 to 2.0 mol relative to 1 mol of the compound represented by general formula (4)), and then reacting in the presence of an oxidizing agent (metachloroperbenzoic acid (m-CPBA) or the like; 1.5 to 10.0 mol, particularly 2.0 to 5.0 mol relative to 1 mol of the compound represented by general formula (4)).

[0108] In addition, R 1 When is a secondary alkyl group, the general formula (4):

[0109] [ka] [In the formula, R 2a is the same as above.] and a compound represented by general formula (5B): R 1a -OH (5B) [In the formula, R 1a represents a secondary alkyl group.] The compound represented by the formula (4) (0.5 to 3.0 moles, particularly 1.0 to 2.0 moles per mole of the compound represented by the formula (4)) is reacted in an organic solvent (tetrahydrofuran (THF) or the like) in the presence of a phosphine catalyst (triphenylphosphine or the like; 0.5 to 3.0 moles, particularly 1.0 to 2.0 moles per mole of the compound represented by the formula (4)) and a dialkyl azodicarboxylate (bis(2-methoxyethyl) azodicarboxylate (DMEAD) or the like; 0.5 to 3.0 moles, particularly 1.0 to 2.0 moles per mole of the compound represented by the formula (4)), and then reacted in the presence of an oxidizing agent (metachloroperbenzoic acid (m-CPBA) or the like; 1.5 to 10.0 moles, particularly 2.0 to 5.0 moles per mole of the compound represented by the formula (4)).

[0110] In addition, R 1 When R is a tertiary alkyl group,1 is a primary alkyl group, or a compound represented by general formula (2A) 1 is a secondary alkyl group, the compound (substrate compound) represented by general formula (2A) is a compound represented by general formula (5A): R 1 -X (5A) [In the formula, R 1 is the same as above. X represents the above halogen atom.] (1.0 to 10.0 mol, particularly 1.5 to 5.0 mol per 1 mol of the substrate compound) in an organic solvent (tetrahydrofuran (THF) or the like) in the presence of a lithium compound (lithium bis(trimethylsilyl)amide (LiHMDS) or the like; 0.5 to 5.0 mol, particularly 1.0 to 4.0 mol per 1 mol of the substrate compound).

[0111] The details of each reaction will be described in the Examples below.

[0112] 3. UV or visible light irradiation In the production method of the present invention, the reaction can be advanced by irradiation with ultraviolet light or visible light.

[0113] Although there is no particular limitation on the type of ultraviolet or visible light irradiation, from the viewpoint of suppressing decomposition of the compound represented by general formula (2A) or (2B) used as a reactant, it is preferable that the wavelength of the irradiated light is not too short, and visible light is more preferable. Furthermore, from the viewpoint of easily and efficiently photoexciting the polycyclic aromatic compound, it is preferable that the visible light used is blue light. For these reasons, the ultraviolet or visible light used has a light source peak wavelength of preferably 300 to 800 nm, more preferably 370 to 525 nm.

[0114] The irradiation intensity of visible light is not particularly limited, but from the viewpoint of easily and efficiently photoexciting the polycyclic aromatic compound, it is preferred to use a light intensity of 10 mW / cm. 2 ~500mW / cm 2 is preferred, and 30 mW / cm 2 ~150mW / cm 2 is more preferred.

[0115] 4. Additives In the production method of the present invention, the reaction can proceed without using any additives, but can also be carried out in the presence of a metal compound and / or an ammonium salt as an additive.

[0116] The metal compound that can be used is not particularly limited, but from the viewpoints of the conversion rate of the reaction, the selectivity for the target product, the yield, etc., alkali metals (lithium, sodium, potassium, cesium, etc.), alkaline earth metals (magnesium, calcium, etc.), zinc, etc. are preferred as the constituent metals.

[0117] The metal compound and / or ammonium salt is not particularly limited, but from the viewpoints of the conversion rate of the reaction, the selectivity for the target product, the yield, and the like, halide salts (chloride salts, bromide salts), acetate salts, tetrafluoroborates, perchlorates, and trifluoromethanesulfonates of the above-mentioned metals and ammonium ions can be used, and chloride salts, acetate salts, trifluoromethanesulfonates, and the like are preferred.

[0118] Specific examples of such additives include lithium chloride, lithium tetrafluoroborate, sodium acetate, potassium acetate, magnesium perchlorate, magnesium trifluoromethanesulfonate, magnesium bromide, zinc chloride, zinc bromide, zinc trifluoromethanesulfonate, zinc acetate, and tetrabutylammonium trifluoromethanesulfonate, and more preferred are lithium chloride, zinc trifluoromethanesulfonate, zinc acetate, and tetrabutylammonium trifluoromethanesulfonate.

[0119] These metal compounds and / or ammonium salts as additives can be used alone or in combination of two or more.

[0120] The amount of the metal compound and / or ammonium salt used as the additive is not particularly limited, but is preferably 1.5 to 10.0 mol, more preferably 2.0 to 5.0 mol, per mol of the polycyclic aromatic compound substrate, from the viewpoints of the reaction conversion rate, selectivity for the target product, yield, etc. When a plurality of metal compounds and / or ammonium salts are used as the additive, it is preferable to adjust the total amount thereof to be within the above range.

[0121] 5. Bases In the production method of the present invention, the reaction can be carried out without using a base, but can also be carried out in the presence of a base.

[0122] The base that can be used is not particularly limited, but carbonates, phosphates, acetates, hydroxides, alkoxides, amines, etc. are preferred, carbonates, phosphates, acetates, etc. are more preferred, and carbonates, phosphates, etc. are even more preferred.

[0123] When the base is a salt, hydroxide, or alkoxide, the cation constituting the base is not particularly limited, but from the viewpoints of the conversion rate of the reaction, the selectivity for the target product, the yield, etc., alkali metals (lithium, sodium, potassium, cesium, etc.) are preferred, and sodium, potassium, etc. are more preferred.

[0124] Specific examples of such bases include lithium carbonate, sodium carbonate, potassium carbonate, cesium carbonate, sodium hydrogencarbonate, potassium phosphate, sodium acetate, potassium acetate, potassium tert-butoxide, sodium hydroxide, triethylamine, etc., of which lithium carbonate, sodium carbonate, potassium carbonate, cesium carbonate, sodium hydrogencarbonate, potassium phosphate, potassium acetate, etc. are preferred, sodium carbonate, potassium carbonate, sodium hydrogencarbonate, potassium phosphate, etc. are more preferred, and sodium carbonate, potassium carbonate, sodium hydrogencarbonate, etc. are even more preferred.

[0125] These bases can be used alone or in combination of two or more.

[0126] The amount of these bases used is not particularly limited, but is preferably 1.5 to 10.0 mol, more preferably 2.0 to 5.0 mol, per mol of the polycyclic aromatic compound substrate, from the viewpoints of reaction conversion rate, selectivity to the target product, yield, etc. When multiple bases are used, it is preferable to adjust the total amount thereof to be within the above range.

[0127] 6. Organic Solvents The reaction of the present invention can usually be carried out in an organic solvent.

[0128] The organic solvent that can be used is not particularly limited, but from the viewpoints of the reaction conversion rate, selectivity for the target product, yield, etc., amide solvents, sulfoxide solvents, etc. are preferred. Examples of amide solvents include N,N-dimethylformamide, N,N-dimethylacetamide, and N-methyl-2-pyrrolidone. Examples of sulfoxide solvents include dimethyl sulfoxide. These organic solvents can be used alone or in combination of two or more.

[0129] The amount of these organic solvents used is not particularly limited, and can be the amount of the solvent.

[0130] 7.Other conditions In the production method of the present invention, the reaction can be carried out under cooling, at room temperature, or under heating, but is usually carried out at 0 to 70° C., preferably 10 to 40° C. Furthermore, in the production method of the present invention, the reaction can be carried out until completion, but is usually carried out for 1 minute to 120 hours, preferably 5 minutes to 96 hours.

[0131] After the production method of the present invention is completed, the target alkyl-substituted polycyclic aromatic compound can be obtained by purification by a conventional method as needed. Specifically, for example, the metal compound can be adsorbed onto silica gel in the reaction mixture, an organic solvent (ethyl acetate, hexane, etc.) is added to dissolve the organic compound in the organic layer, and then the mixture is concentrated under reduced pressure to purify the product. Alternatively, purification can be performed using a preparative HPLC equipped with gel permeation chromatography (GPC). [Example]

[0132] The present invention will be specifically explained below by way of examples, but the present invention is not limited thereto.

[0133] Unless otherwise noted, all materials, including dry solvents, were purchased commercially and used without purification. 2-tert-butylpyrene (Compound 1a), 1-bromo-7-tert-butylpyrene, 2-triethylsilylpyrene (Compound 1d), 2-(propylsulfonyl)benzothiazole, and 2,2-dimethyl-1,3-dihydro-1,3-dioxo-2H-isoindol-2-ylbutanoic acid ester were synthesized as previously described. Unless otherwise noted, all reactions were carried out using standard vacuum line techniques in flame-dried glassware under an argon atmosphere with dry solvents. All workups and purification procedures were carried out in air using reagent-grade solvents.

[0134] Analytical thin-layer chromatography (TLC) was performed on Merck silica gel 60F with visualization by ultraviolet light (254 nm). 254 Preparative thin-layer chromatography (PTLC) was performed using precoated plates (0.25 mm) and ethanolic phosphomolybdic acid. Preparative thin-layer chromatography (PTLC) was performed using Wakogel B5-F silica-coated plates (0.75 mm). Preparative recycling HPLC was performed using a JAI LC-9204 equipped with a JAIGEL-1H / JAIGEL-2H column, using chloroform or ethyl acetate as the eluent.

[0135] High-resolution mass spectra (HRMS) were obtained using a Thermo Fisher Scientific Exactive (ESI) and a JMS-T100TD (DART). Nuclear magnetic resonance (NMR) spectra were obtained using a JEOL ECA600II ( 1 H 600 MHz, 13 C 150 MHz), JEOL ECS-400( 1 H 400 MHz, 13 C 100 MHz, 19 F 376 MHz, 31 P 160 MHz) spectrometer. 1 Chemical shifts for 1 H NMR spectra are expressed in parts per million (ppm) relative to tetramethylsilane (δ 0.00 ppm) or CD3OD (δ 3.31 ppm). 13 Chemical shifts for C NMR spectra are expressed in parts per million (ppm) relative to CDCl (δ 77.0 ppm). Data are reported as chemical shift, multiplicity (s = singlet, d = doublet, t = triplet, q = quartet, quin = quintet, m = multiplet), coupling constant (Hz), and integration.

[0136] Gas chromatography (GC) analysis was performed on a Shimadzu GC-2010 equipped with an HP-5 column (30 m × 0.25 mm, Hewlett-Packard). GC-MS analysis was performed on a Shimadzu GC-2010 equipped with an HP-5 column (30 m × 0.25 mm, Hewlett-Packard). LC-MS analysis was performed on a Shimadzu LC-MS 2020 equipped with a ZORBAX Eclipse PAH column (4.6 × 150 mm, 3.5 μm, Agilent Technologies) using acetonitrile / HO as the eluent.

[0137] UV-visible absorption spectra were recorded on a Shimadzu UV-1800 spectrometer using a 1 cm quartz cuvette, and fluorescence spectra were measured on a SPEX Fluorolog 3 spectrofluorometer (Horiba).

[0138] The photocatalytic reaction was carried out under the irradiation of Kessil (registered trademark; PR 160L) as an LED light source. In this setup, a fan was used to maintain the reaction temperature at approximately 30–35 °C.

[0139] [Synthesis Example 1: Polycyclic aromatic compound] Synthesis Example 1-1: 2-Mesitylpyrene

[0140] [ka] A 100 mL flask containing a magnetic stir bar was flame-dried under vacuum, cooled to room temperature, and then backfilled with argon. 4,4,5,5-tetramethyl-2-(pyren-2-yl)-1,3,2-dioxaborolane (330 mg, 1.0 mmol), 2,4,6-trimethylbromobenzene (0.22 mL, 1.5 mmol), tetrakis(triphenylphosphine)palladium (Pd(PPh3)4; 120 mg, 0.10 mmol), and K2CO3 (410 mg, 3.0 mmol) were added to the flask in toluene (16 mL), ethanol (8 mL), and degassed water (8 mL). The reaction mixture was vigorously stirred under argon at 110 °C for 24 h. After cooling to room temperature, the solvent was evaporated, and the residue was diluted with CHCl2 and washed with water. The combined extracts were dried over Na2SO4, filtered, and evaporated under reduced pressure. The residue was purified by column chromatography (hexane:CH2Cl2=100:1 to 15:1) to give 2-mesitylpyrene (260 mg, 62%) as a white solid. 1H NMR (600 MHz, CDCl3) δ 2.02 (s, 6H), 2.39 (s, 3H), 7.03 (s, 2H), 7.96 (s, 1H), 7.98 (d, J = 7.8 Hz, 2H), 8.04 (d, J = 9.0 Hz, 2H), 8.07 (d, J = 9.0 Hz, 2H), 8.17 (d, J = 7.8 Hz, 2H). 13 C NMR (150 MHz, CDCl3) δ 21.0, 21.1, 123.5, 124.6, 125.0, 125.8, 125.9, 127.4, 127.5, 128.1, 131.0, 131.3, 136.2, 136.8, 138.9, 139.1. HRMS (DART) m / z calcd for C 25 H 21 [M+H] + : 321.1643, found 321.1646.

[0141] Synthesis Example 1-2: 2-tert-butyl-6-(2'-methyl-1',3'-dioxolan-2-yl)pyrene

[0142] [ka] A 500 mL flask equipped with a magnetic stir bar was flame-dried under vacuum, cooled to room temperature, and then backfilled with argon. To this flask, under argon, was added 2-tert-butylpyrene (5.16 g, 20 mmol) and dry CHCl (80 mL). To the resulting mixture, acetyl chloride (1.6 mL, 22 mmol) and AlCl (2.94 g, 22 mmol) were added at 0 °C, and the mixture was stirred at room temperature for 16 h. The mixture was quenched with water and extracted with CHCl (3 times). The combined extracts were dried over NaSO, filtered, and evaporated under reduced pressure. The residue was purified by column chromatography (ethyl acetate:hexane = 1:30) to give 2-tert-butyl-6-acetylpyrene (4.54 g, 76%) as a yellow solid. 1H NMR (600 MHz, CDCl3) δ 1.59 (s, 9H), 2.91 (s, 3H), 8.06 (d, J= 9.0 Hz, 1H), 8.156 (d, J = 7.8 Hz, 1H), 8.163 (d, J = 9.0 Hz, 1H), 8.22 (d, J = 9.6 Hz, 1H), 8.29 (d, J = 2.4 Hz, 1H), 8.30 (d, J = 2.4 Hz, 1H), 8.38 (d, J = 7.8 Hz, 1H), 9.07 (d, J = 9.6 Hz, 1H). 13 C NMR (150 MHz, CDCl3) δ 30.4, 31.9, 35.2, 122.5, 123.3, 123.7, 123.8, 124.86, 124.90, 126.90, 126.94, 129.3, 129.9, 130.0, 130.4, 130.9, 131.6, 133.9, 149.6, 202.2. HRMS (ESI) m / z calcd for C 22 H 21 O [M+H] + : 301.1587, found 301.1588.

[0143] In a 200 mL flask equipped with a Dean-Stark apparatus, 2-tert-butyl-6-acetylpyrene (2.24 g, 7.5 mmol), ethylene glycol (4.2 mL, 75 mmol, 10 equiv.), and p-toluenesulfonic acid monohydrate (0.14 g, 0.75 mmol) were added to toluene (38 mL). The mixture was stirred at reflux for 16 h. K2CO3 (4 g) was added to the mixture, which was stirred at room temperature for 1 h. Water was then added and the mixture was extracted with ethyl acetate (3 times). The combined extracts were dried over Na2SO4, filtered, and evaporated under reduced pressure. The residue was purified by column chromatography (ethyl acetate:hexane = 1:50) to give 2-tert-butyl-6-(2'-methyl-1',3'-dioxolan-2-yl)pyrene (1.86 g, 72%) as a pale yellow solid. 1H NMR (600 MHz, CDCl3) δ 1.57 (s, 9H), 2.01 (s, 3H), 3.83-3.85 (m, 2H), 4.14-4.17 (m, 2H), 8.00 (d, J = 9.0 Hz, 1H), 8.02 (d, J = 8.4 Hz, 1H), 8.090 (d, J = 9.0 Hz, 1H), 8.091 (d, J = 9.0 Hz, 1H), 8.20 (d, J = 2.4 Hz, 1H), 8.22 (d, J = 2.4 Hz, 1H), 8.26 (d, J = 8.4 Hz, 1H), 8.86 (d, J = 9.6 Hz, 1H). 13 C NMR (150 MHz, CDCl3) δ 28.0, 31.9, 35.2, 64.2, 110.1, 122.3, 122.4, 123.0, 123.5, 124.2, 125.3, 125.5, 127.2, 127.4, 127.7, 127.8, 130.4, 131.1, 131.2, 136.1, 149.0. HRMS (ESI) m / z calcd for C 24 H 25 O2[M+H] + : 345.1849, found 345.1850.

[0144] Synthesis Example 1-3: 2-tert-butyl-6-chloropyrene

[0145] [ka] A 20 mL flask containing a magnetic stir bar was flame dried under vacuum, cooled to room temperature, and then backfilled with argon. To this flask, under argon, was added 2-tert-butylpyrene (51.7 mg, 0.20 mmol), CuCl (59.2 mg, 0.44 mmol), and dry chlorobenzene (2 mL). The mixture was refluxed for 3 h. The mixture was passed through a pad of silica gel, washed successively with ethyl acetate, and the filtrate was concentrated under reduced pressure. The residue was purified by gel permeation chromatography (GPC) to give 2-tert-butyl-6-chloropyrene (38.7 mg, 66%) as a pale orange solid. 1 1H NMR (400 MHz, CDCl3) δ 1.58 (s, 9H), 7.98 (d, J = 9.2 Hz, 1H), 7.99 (d, J = 8.0 Hz, 1H), 8.031 (d, J = 8.0 Hz, 1H), 8.035 (d, J = 9.2 Hz, 1H), 8.14 (d, J = 9.2 Hz, 1H), 8.24 (d, J = 2.0 Hz, 2H), 8.41 (d, J = 9.2 Hz, 1H). 13 13C NMR (150 MHz, CDCl3) δ 31.9, 35.2, 122.3, 122.7, 123.1, 125.0, 125.6, 126.3, 126.9, 127.7, 127.9, 128.8, 129.8, 130.8, 131.0, 149.7. HRMS (DART) m / z calcd for C 20 1H 18 Cl [M+H] + : 293.1097, found 293.1096。

[0146] Synthesis Example 1-4: 2-tert-butyl-6-(trimethylsilyl)pyrene

[0147]

Chem.

[0148] Synthesis Example 1-5: 3,8-dimethyl-1-(2'-methyl-1',3'-dioxolan-2-yl)pyrene

[0149] [ka] A 500 mL flask containing a magnetic stir bar was flame dried under vacuum, cooled to room temperature, and then backfilled with argon. 1,6-Dibromopyrene (1.08 g, 3 mmol) and dry 1,2-dichloroethane (140 mL) were added to the flask, and the mixture was stirred at 80 °C (oil bath) until the pyrene compound was completely dissolved. The oil bath was removed, and acetyl chloride (230 μL, 3.3 mmol) and AlCl (441 mg, 3.3 mmol) were added sequentially. The mixture was stirred at room temperature for 16 h. The mixture was quenched with 6 N aqueous HCl and extracted with CHCl (3 times). The combined extracts were dried over NaSO, filtered, and evaporated under reduced pressure. The residue was purified by column chromatography (CH2Cl2:hexane = 1:3 to 1:2) to give 3-acetyl-1,6-dibromopyrene (1.09 g, 90%) as a yellow solid. 1 H NMR (400 MHz, CDCl3) δ 2.91 (s, 3H), 8.12 (d, J = 8.4 Hz, 1H), 8.22 (d, J = 9.2 Hz, 1H), 8.33 (d, J = 8.4 Hz, 1H), 8.48 (d, J = 9.6 Hz, 1H), 8.59 (d, J = 9.6 Hz, 1H), 8.64 (s, 1H), 9.04 (d, J = 9.2 Hz, 1H). 13 C NMR (150 MHz, CDCl3) δ 30.5, 119.7, 122.1, 124.8, 125.6, 126.0, 126.2, 127.2, 128.4, 128.6, 129.2, 130.3, 130.8, 131.3, 131.5, 132.3, 132.8, 200.6. HRMS (DART) m / z calcd for C 18 H 11 Br2O [M+H]+ : 400.9177, found 400.9183.

[0150] A 100 mL flask containing a magnetic stir bar was flame-dried under vacuum, cooled to room temperature, and then backfilled with argon. 3-acetyl-1,6-dibromopyrene (436 mg, 1.1 mmol), tetrakis(triphenylphosphine)palladium (Pd(PPh3)4; 63 mg, 0.054 mmol), Na2CO3 (1.04 g, 9.8 mmol), dioxane (10 mL), degassed water (2 mL), and trimethylboroxine (910 μL, 6.5 mmol) were added to the flask. The mixture was stirred at 100 °C for 18 h. The mixture was passed through a pad of silica gel, washed successively with ethyl acetate, and the filtrate was concentrated under reduced pressure. The residue was purified by column chromatography (CHCl2:hexane = 1:1 - 2:1) to give 1-acetyl-3,8-dimethylpyrene (213 mg, 72%) as a pale yellow solid. 1 H NMR (600 MHz, CDCl3) δ 2.89 (s, 3H), 2.96 (s, 3H), 2.98 (s, 3H), 7.87 (d, J = 7.8 Hz, 1H), 8.10 (d, J = 7.8 Hz, 1H), 8.12 (s, 2H), 8.19 (s, 1H), 8.30 (d, J = 9.6 Hz, 1H), 9.01 (d, J = 9.6 Hz, 1H). 13 C NMR (150 MHz, CDCl3) δ 20.0, 20.2, 30.5, 122.3, 124.55, 124.61, 125.0, 125.3, 125.9, 127.9, 128.3, 128.8, 128.9, 129.4, 129.5, 130.7, 131.3, 132.4, 133.5, 202.3. HRMS (ESI) m / z calcd for C 20 H 17 O [M+H] + : 273.1274, found 273.1274.

[0151] A 50 mL flask equipped with a Dean-Stark apparatus was charged with 1-acetyl-3,8-dimethylpyrene (200 mg, 0.74 mmol), ethylene glycol (0.20 mL, 3.7 mmol), p-toluenesulfonic acid monohydrate (7.0 mg, 0.04 mmol), and toluene (7 mL). The mixture was stirred at reflux for 16 hours. K2CO3 (0.25 g) was added to the mixture, which was stirred at room temperature for 1 hour. Water was then added, and the mixture was extracted with ethyl acetate (3 times). The combined extracts were dried over Na2SO4, filtered, and evaporated under reduced pressure. The residue was purified by column chromatography (ethyl acetate:hexane = 1:50) to give 3,8-dimethyl-1-(2'-methyl-1',3'-dioxolan-2-yl)-pyrene (160 mg, 70%) as a pale yellow solid. 1 H NMR (600 MHz, CDCl3) δ 2.01 (s, 3H), 2.90 (s, 3H), 2.92 (s, 3H), 3.78-3.81 (m, 2H), 4.07-4.11 (m, 2H), 7.75 (d, J = 7.8 Hz, 1H), 7.94 (d, J = 9.0 Hz, 1H), 7.97 (d, J = 7.8 Hz, 1H), 8.05 (d, J = 9.0 Hz, 1H), 8.15 (s, 1H), 8.17 (d, J = 9.6 Hz, 1H), 8.89 (d, J = 9.6 Hz, 1H). 13 C NMR (150 MHz, CDCl3) δ 19.8, 20.2, 28.0, 64.2, 110.0, 122.4, 124.6, 125.0, 125.8, 126.0, 126.3, 127.4, 127.7, 128.7, 129.56, 129.60, 131.2, 132.1, 135.4. HRMS (ESI) m / z calcd for C 22 H 21 O2 [M+H] + : 317.1536, found 317.1538.

[0152] Synthesis Example 1-6: 1,3,6-tris(2'-methyl-1',3'-dioxolan-2-yl)pyrene

[0153] [ka] A 50 mL flask containing a magnetic stir bar was flame-dried under vacuum, cooled to room temperature, and backfilled with argon. 3-acetyl-1,6-dibromopyrene (600 mg, 1.5 mmol), palladium acetate (Pd(OAc)2; 25.3 mg, 0.15 mmol), 1,1'-bis(diphenylphosphino)ferrocene (dppf; 105 mg, 0.25 mmol), K2CO3 (497 mg, 3.6 mmol), dimethylformamide (DMF; 4 mL), degassed water (1 mL), and butyl vinyl ether (1.15 mL, 9 mmol) were added to the flask. The mixture was stirred at 90 °C for 48 h. The mixture was quenched with 2 N aqueous HCl and extracted with CHCl2 (3 times). The combined extracts were dried over Na2SO4, filtered, and evaporated under reduced pressure. The residue was purified by column chromatography (CH2Cl2:hexane = 1:1 to 1:0) to give 1,3,6-triacetylpyrene (404 mg, 58%) as a yellow solid. 1 H NMR (600 MHz, CDCl3) δ 2.92 (s, 3H), 2.95 (s, 6H), 8.21 (d, J= 8.4 Hz, 1H), 8.27 (d, J = 8.4 Hz, 1H), 8.42 (d, J = 7.8 Hz, 1H), 8.66 (s, 1H), 8.93 (d, J = 10.2 Hz, 1H), 8.95 (d, J = 7.8 Hz, 1H), 9.07 (d, J = 10.2 Hz, 1H). 13 C NMR (150 MHz, CDCl3) δ 30.6, 30.7, 124.4, 126.4, 127.42, 127.45, 128.4, 128.8, 130.6, 131.0, 131.5, 132.4, 132.5, 132.8, 134.3, 201.50, 201.53, 202.0. HRMS (ESI) m / z calcd for C 22 H17 O3 [M+H] + : 329.1172, found 329.1172.

[0154] A 200 mL flask equipped with a Dean-Stark apparatus was charged with 1,3,6-triacetylpyrene (400 mg, 1.2 mmol), ethylene glycol (2.7 mL, 49 mmol), p-toluenesulfonic acid monohydrate (69.5 mg, 0.4 mmol), and toluene (48 mL). The mixture was refluxed for 16 hours. K2CO3 (4 g) was added to the mixture, which was stirred at room temperature for 1 hour. Water was then added, and the mixture was extracted with ethyl acetate (three times). The combined extracts were dried over Na2SO4, filtered, and evaporated under reduced pressure. The residue was purified by column chromatography (ethyl acetate:hexane = 1:10 - 1:8) to give 1,3,6-tris(2'-methyl-1',3'-dioxolan-2-yl)pyrene (320 mg, 57%) as a pale yellow solid. 1 H NMR (600 MHz, CDCl3) δ 2.017 (s, 3H), 2.021 (s, 3H), 2.04 (s, 3H), 3.82-3.86 (m, 2H), 4.14-4.19 (m, 2H), 8.05 (d, J = 9.6 Hz, 1H), 8.12 (d, J = 7.8 Hz, 1H), 8.30 (d, J = 7.8 Hz, 1H), 8.63 (s, 1H), 8.89 (d, J = 9.6 Hz, 1H), 8.94 (d, J = 9.6 Hz, 1H), 8.96 (d, J = 9.6 Hz, 1H). 13 C NMR (150 MHz, CDCl3) δ 28.05, 28.08, 64.2, 64.3, 1110.0, 110.06, 110.10, 121.8, 124.0, 124.8, 125.0, 125.2, 125.3, 125.9, 126.9, 127.2, 127.5, 127.7, 128.4, 130.8, 135.56, 135.64, 136.6. HRMS (ESI) m / z calcd for C 28 H29 O6 [M+H] + : 461.1959, found 461.1958.

[0155] Synthesis Example 1-7: N-pivaloylbenzo[f]indole

[0156] [ka] A 30 mL flask containing a magnetic stir bar was flame-dried under vacuum, cooled to room temperature, and then backfilled with argon. Benzo[f]indole (167 mg, 1 mmol), 4-dimethylaminopyridine (DMAP; 12.4 mg, 0.1 mmol), CHCl (3 mL), and triethylamine (NEt; 210 μL, 1.5 mmol) were added to the flask. Pivaloyl chloride (150 μL, 1.2 mmol) was added to the mixture at 0 °C and stirred at room temperature for 16 h. The mixture was quenched with saturated aqueous NHCl and extracted with CHCl (3×). The combined extracts were dried over NaSO, filtered, and evaporated under reduced pressure. The residue was purified by column chromatography (ethyl acetate:hexane = 1:10) to afford N-pivaloylbenzo[f]indole (166 mg, 66%) as a white solid. 1 H NMR (600 MHz, CDCl3) δ 1.53 (s, 9H), 6.71 (d, J = 4.2 Hz, 1H), 7.41-7.45 (m, 2H), 7.85 (d, J = 4.2 Hz, 1H), 7.89-7.90 (m, 1H), 7.98-7.99 (m, 2H), 9.08 (s, 1H). 13 C NMR (150 MHz, CDCl3) δ 28.6, 41.0, 108.4, 114.9, 118.2, 124.6, 124.8, 127.7, 128.5, 128.8, 129.7, 130.6, 132.1, 136.1, 176.6. HRMS (ESI) m / zcalcd for C 17 H 18 ON [M+H] +: 252.1383, found 252.1383.

[0157] [Synthesis Example 2: Alkyl sulfone compounds] Synthesis Examples 2-1 to 2-7: Primary alkyl sulfone compounds (using alkyl halides) (common operation)

[0158] [ka] A flask containing a magnetic stir bar was flame-dried under vacuum, cooled to room temperature, and backfilled with argon. To this flask, under argon, was added the aryl thiol compound (1 equiv.), alkyl bromide (1.3 equiv.), and dry tetrahydrofuran (THF; 4 mL per 1 mmol of aryl thiol compound). Diazabicycloundecene (DBU; 1.5 equiv.) was added, and the mixture was stirred at room temperature for 16 h. The mixture was quenched with saturated aqueous NH4Cl and extracted with ethyl acetate (3 times). The combined extracts were dried over Na2SO4, filtered, and evaporated under reduced pressure. The residue was dissolved in CHCl2 (1 mL per 1 mmol of aryl thiol compound). To this solution, a solution of metachloroperbenzoic acid (mCPBA; >65%, 2.5 equiv.) in CHCl2 (4 mL per 1 mmol of aryl thiol compound) was slowly added at 0 °C, and the mixture was stirred at room temperature for 16 h. The mixture was quenched with saturated Na2SO3 solution and washed with saturated aqueous NaHCO3 (3 times). The organic layer was dried over Na2SO4, filtered, and evaporated under reduced pressure. The residue was purified by column chromatography to give the corresponding primary alkyl sulfone compound.

[0159] Note: For the synthesis of 1-p-anisyl-5-((3'-tert-butyldimethylsilyl)oxypropyl)-1H-tetrazole, oxidation was carried out as follows: The residue was dissolved in ethyl acetate (8 mL per 1 mmol of aryl thiol compound), and NaWO4·2H2O (0.05 equiv.) and tetrabutylammonium bromide (Bu4NBr; 0.15 equiv.) were added. To this solution, H2O2 (30% aqueous solution, 3 equiv.) was slowly added at 0 °C, and the mixture was stirred at room temperature for 16 h. The mixture was quenched with saturated Na2SO3 solution and passed through a pad of silica gel, washing successively with ethyl acetate (ca. 10 mL). The filtrate was concentrated under reduced pressure. The residue was purified by column chromatography to give the corresponding primary alkyl sulfone compound.

[0160] (Synthesis Example 2-1) 1-phenyl-5-propylsulfonyl-1H-tetrazole

[0161] [ka] The product was purified by column chromatography (ethyl acetate:hexane = 1:5) to give the target compound as a white solid (2.31 g, 92% isolated yield, 10 mmol scale). 1 H NMR (600 MHz, CDCl3) δ 1.14 (t, J = 7.8 Hz, 3H), 1.98-2.05 (m, 2H), 3.71-3.74 (m, 2H), 7.59-7.65 (m, 3H), 7.69-7.70 (m, 2H). 13 C NMR (150 MHz, CDCl3) δ 12.8, 16.0, 57.5, 125.0, 129.7, 131.5, 133.0, 153.4. HRMS (ESI) m / z calcd for C 10 H 12 O2N4NaS [M+Na] + : 275.0573, found 275.0571.

[0162] (Synthesis Example 2-2) 5-propylsulfonyl-1-(p-trifluoromethylphenyl)-1H-tetrazole

[0163] [ka] The product was purified by column chromatography (ethyl acetate:hexane = 1:8) to give the target compound as a white solid (969 mg, 75% isolated yield, 4 mmol scale). 1 H NMR (600 MHz, CDCl3) δ 1.16 (t, J = 7.5 Hz, 3H), 2.00-2.05 (m, 2H), 3.75-3.78 (m, 2H), 7.89 (s, 4H). 13 C NMR (150 MHz, CDCl3) δ 12.7, 15.9, 57.5, 123.1 (q, J = 271.0 Hz), 125.5, 127.0 (q, J = 4.4 Hz), 133.3 (q, J = 33.5 Hz), 135.7, 153.5. 19 F NMR (376 MHz, CDCl3) δ -62.8. HRMS (ESI) m / zcalcd for C 11 H 11 O2N4F3NaS [M+Na] + : 343.0447, found 343.0449.

[0164] (Synthesis Example 2-3) 1-p-anisyl-5-propylsulfonyl-1H-tetrazole

[0165] [ka] The product was purified by column chromatography (ethyl acetate:hexane = 1:6) to obtain the target compound as a pale yellow solid (5.40 g, 96% isolated yield, 20 mmol scale). 1H NMR (400 MHz, CDCl3) δ 1.13 (t, J = 7.2 Hz, 3H), 1.95-2.05 (m, 2H), 3.68-3.72 (m, 2H), 3.89 (s, 3H), 7.06 (dm, J = 9.2 Hz, 2H), 7.59 (dm, J = 9.2 Hz, 2H). 13 C NMR (150 MHz, CDCl3) δ 12.8, 15.9, 55.6, 57.4, 114.7, 125.5, 126.5, 153.3, 161.6. HRMS (ESI) m / z calcd for C 11 H 14 O3N4NaS [M+Na] + : 305.0679, found 305.0678.

[0166] (Synthesis Example 2-4) 2-(Propylsulfonyl)pyridine

[0167] [ka] The product was purified by column chromatography (ethyl acetate:hexane = 1:3) to give the target compound as a pale yellow solid (804 mg, 87% isolated yield, 5 mmol scale). 1 H NMR (600 MHz, CDCl3) δ 1.03 (t, J = 7.5 Hz, 3H), 1.75-1.82 (m, 2H), 3.37-3.39 (m, 2H), 7.57 (ddd, J = 1.8, 4.8, 7.2 Hz, 1H), 7.98 (dt, J = 1.8, 7.2 Hz, 1H), 8.10 (d, J = 7.2 Hz, 1H), 8.76 (d, J= 4.8 Hz, 1H). 13 C NMR (150 MHz, CDCl3) δ 13.0, 15.9, 53.5, 122.1, 127.3, 138.1, 150.2, 157.2. HRMS (ESI) m / z calcd for C8H 11 O2NNaS [M+Na] +: 208.0403, found 208.0404.

[0168] (Synthesis Example 2-5) 1-p-anisyl-5-(3'-phenylpropylsulfonyl)-1H-tetrazole

[0169] [ka] The product was purified by column chromatography (ethyl acetate:hexane = 1:5) to give the target compound as a white solid (2.97 g, 83% isolated yield, 10 mmol scale). 1 H NMR (600 MHz, CDCl3) δ 2.26-2.31 (m, 2H), 2.82 (t, J = 7.8 Hz, 2H), 3.66-3.68 (m, 2H), 3.87 (s, 3H), 7.04 (dm, J = 9.0 Hz, 2H), 7.18 (d, J = 7.2 Hz, 2H), 7.23 (d, J = 7.2 Hz, 1H), 7.31 (d, J= 7.2 Hz, 2H), 7.54 (dm, J = 9.0 Hz, 2H). 13 C NMR (150 MHz, CDCl3) δ 23.5, 33.8, 55.0, 55.6, 114.7, 125.5, 126.5, 126.6, 128.4, 128.7, 139.2, 153.3, 161.6. HRMS (ESI) m / z calcd for C 17 H 18 O3N4NaS [M+Na] + : 381.0992, found 381.0992.

[0170] (Synthesis Example 2-6) 1-p-anisyl-5-(3'-tert-butyldimethylsilyl)oxypropylsulfonyl)-1H-tetrazole

[0171] [ka] The product was purified by column chromatography (ethyl acetate:hexane = 1:15) to give the target product as a viscous liquid (6.23 g, 91% isolated yield, 20 mmol scale). 1 H NMR (600 MHz, CDCl3) δ 0.06 (s, 6H), 0.89 (s, 9H), 2.14-2.17 (m, 2H), 3.78 (t, J = 6.0 Hz, 2H), 3.81-3.84 (m, 2H), 3.89 (s, 3H), 7.06 (dm, J = 9.0 Hz, 2H), 7.59 (dm, J = 9.0 Hz, 2H). 13 C NMR (150 MHz, CDCl3) δ -5.5, 18.2, 25.5, 25.8, 53.2, 55.7, 60.3, 114.7, 125.6, 126.5, 153.3, 161.6. HRMS (ESI) m / zcalcd for C 17 H 28 O4N4NaSSi [M+Na] + : 435.1493, found 435.1495.

[0172] (Synthesis Example 2-7) 1-p-anisyl-5-(1'-(ethoxycarbonylmethyl)sulfonyl)-1H-tetrazole

[0173] [ka] The product was purified by column chromatography (ethyl acetate:hexane = 1:5) to give the target compound as a white solid (1.40 g, 86% isolated yield, 5 mmol scale). 1 H NMR (600 MHz, CDCl3) δ 1.24 (t, J = 7.2 Hz, 3H), 3.89 (s, 3H), 4.21 (q, J = 7.2 Hz, 2H), 4.64 (s, 2H), 7.06 (dm, J = 9.0 Hz, 2H), 7.56 (dm, J = 9.0 Hz, 2H). 13C NMR (150 MHz, CDCl3) δ 13.8, 55.7, 59.3, 63.1, 114.6, 125.4, 126.9, 153.1, 161.1, 161.8. HRMS (ESI) m / z calcd for C 12 H 14 O5N4NaS [M+Na] + : 349.0577, found 349.0576.

[0174] Synthesis Examples 2-8 to 2-11: Secondary alkyl sulfone compounds (using alkyl halides) (common operation)

[0175] [ka] A flask containing a magnetic stir bar was flame-dried under vacuum, cooled to room temperature, and backfilled with argon. To this flask, under argon, was added 5-mercapto-1-(4-methoxyphenyl)-1H-tetrazole (1 equivalent), K2CO3 (2 equivalents), and dry acetone (3 mL per 1 mmol of aryl thiol compound). The alkyl halide was added to the mixture, and the mixture was refluxed for 16 h. The solvent was evaporated under reduced pressure, and ethyl acetate was added. The mixture was filtered and evaporated under reduced pressure. The residue was dissolved in CHCl2 (1 mL per 1 mmol of aryl thiol compound). A solution of metachloroperbenzoic acid (mCPBA; >65%, 2.5 equivalents) in CHCl2 (4 mL per 1 mmol of aryl thiol compound) was slowly added to this solution at 0 °C, and the mixture was stirred at room temperature for 16 h. The mixture was quenched with saturated Na2SO3 solution and washed with saturated aqueous NaHCO3 (3 times). The organic layer was dried over Na2SO4, filtered, and evaporated under reduced pressure. The residue was purified by column chromatography to give the corresponding secondary alkyl sulfone compound.

[0176] (Synthesis Example 2-8) 1-p-anisyl-5-isopropylsulfonyl-1H-tetrazole

[0177] [ka] Isopropyl iodide (1.5 equivalents) was used. The product was purified by column chromatography (ethyl acetate:hexane = 1:6). The target product was obtained as a colorless liquid (2.62 g, 94% isolated yield, 10 mmol scale). 1 H NMR (600 MHz, CDCl3) δ 1.51 (d, J = 6.6 Hz, 6H), 3.89 (s, 3H), 4.00 (quint, J = 6.6 Hz, 1H), 7.06 (dm, J = 9.0 Hz, 2H), 7.57 (dm, J = 9.0 Hz, 2H). 13 C NMR (150 MHz, CDCl3) δ 14.9, 55.6, 56.6, 114.6, 125.6, 126.7, 152.4, 161.6. HRMS (ESI) m / z calcd for C 11 H 14 O3N4NaS [M+Na] + : 305.0679, found 305.0679.

[0178] (Synthesis Example 2-9) 1-p-anisyl-5-(2-butyl)sulfonyl-1H-tetrazole

[0179] [ka] 2-Bromobutane (1.1 equivalents) was used. Purification was carried out by column chromatography (ethyl acetate:hexane = 1:5). The target product was obtained as a colorless liquid (5.17 g, 87% isolated yield, 20 mmol scale). 1 H NMR (600 MHz, CDCl3) δ 1.08 (t, J = 7.8 Hz, 3H), 1.48 (t, J= 7.8 Hz, 3H), 1.69 (m, 1H), 2.12 (m, 1H), 3.76 (m, 1H), 3.88 (s, 3H), 7.06 (dm, J = 9.0 Hz, 2H), 7.56 (dm, J = 9.0 Hz, 2H). 13C NMR (150 MHz, CDCl3) δ 10.6, 11.9, 21.7, 55.5, 62.0, 114.4, 125.5, 126.7, 152.6, 161.5. HRMS (ESI) m / zcalcd for C 12 H 17 O3N4S [M+H] + : 297.1016, found 297.1016.

[0180] (Synthesis Example 2-10) 1-p-anisyl-5-(1'-(1'-(ethoxycarbonylethyl))sulfonyl)-1H-tetrazole

[0181] [ka] Ethyl 1-bromopropionate (1.1 equivalents) was used. The product was purified by column chromatography (ethyl acetate:hexane = 1:5). The target product was obtained as a colorless liquid (2.26 g, 60% isolated yield, 10 mmol scale). 1 H NMR (600 MHz, CDCl3) δ 1.19 (t, J = 7.2 Hz, 3H), 1.79 (d, J= 7.2 Hz, 3H), 3.89 (s, 3H), 4.16 (q, J = 7.2 Hz, 2H), 4.69 (q, J= 7.2 Hz, 1H), 7.06 (dm, J = 9.0 Hz, 2H), 7.54 (dm, J = 9.0 Hz, 2H). 13 C NMR (150 MHz, CDCl3) δ 10.1, 13.7, 55.7, 63.0, 65.1, 114.5, 125.4, 127.0, 152.9, 161.7, 164.5. HRMS (ESI) m / zcalcd for C 13 H 17 O5N4S [M+H] + : 341.0914, found 341.0915.

[0182] (Synthesis Example 2-11) 1-p-anisyl-5-(N,N-dimethylaminocarbonylmethyl)sulfonyl-1H-tetrazole

[0183] [ka] 2-Bromo-N,N-dimethylacetamide (1.2 equivalents) was used. Purification was carried out by column chromatography (ethyl acetate:hexane = 1:1). The target product was obtained as a white solid (1.39 g, 57% isolated yield, 7.5 mmol scale). 1 H NMR (400 MHz, CDCl3) δ 2.91 (s, 3H), 3.07 (s, 3H), 3.89 (s, 3H), 4.67 (s, 2H), 7.04 (dm, J = 9.2 Hz, 2H), 7.60 (dm, J = 9.2 Hz, 2H). 13 C NMR (150 MHz, CDCl3) δ 35.7, 37.8, 55.6, 58.8, 114.4, 125.6, 127.4, 153.5, 160.1, 161.6. HRMS (ESI) m / zcalcd for C 12 H 16 O4N5S [M+H] + : 326.0918, found 326.0919.

[0184] Synthesis Example 2-12: p-anisyl-5-(1'-(ethoxycarbonylethyl))sulfonyl-1H-tetrazole

[0185] [ka] A 100 mL flask containing a magnetic stir bar was flame dried under vacuum, cooled to room temperature, and backfilled with argon. To this flask, under argon, was added 5-mercapto-1-(4-methoxyphenyl)-1H-tetrazole (2.08 g, 10 mmol) and dry CHCl (30 mL). Ethyl 2-bromopropionate (1.36 mL, 10.5 mmol) and triethylamine (NEt; 1.6 mL, 11 mmol) were added to the mixture and stirred at room temperature. The mixture was quenched with saturated aqueous NHCl and extracted with CHCl (3×). The combined extracts were dried over NaSO, filtered, and evaporated under reduced pressure. The residue was dissolved in CHCl (10 mL). To this solution, a solution of metachloroperbenzoic acid (mCPBA; >65%, 5.61 g, 25 mmol) in CHCl (40 mL) was slowly added at 0 °C, and the mixture was stirred at room temperature for 16 h. The mixture was quenched with saturated NaSO solution and washed with saturated aqueous NaHCO (3 times). The organic layer was dried over NaSO, filtered, and evaporated under reduced pressure. The residue was purified by column chromatography (ethyl acetate:hexane = 1:5) to give p-anisyl-5-(1'-(ethoxycarbonylethyl))sulfonyl-1H-tetrazole (2.26 g, 66%, 2 steps) as a colorless oil. 1 H NMR (600 MHz, CDCl3) δ 1.19 (t, J = 7.2 Hz, 3H), 1.79 (d, J= 7.2 Hz, 3H), 3.89 (s, 3H), 4.16 (q, J = 7.2 Hz, 2H), 4.69 (q, J= 7.2 Hz, 1H), 7.06 (dm, J = 9.0 Hz, 2H), 7.54 (dm, J = 9.0 Hz, 2H). 13 C NMR (150 MHz, CDCl3) δ 10.1, 13.7, 55.7, 63.0, 65.1, 114.5, 125.4, 127.0, 152.9, 161.7. HRMS (ESI) m / zcalcd for C 13 H 17 O5N4S [M+H] +: 341.0914, found 341.0915.

[0186] Synthesis Examples 2-13 to 2-16: Secondary alkyl sulfone compounds (using alcohol) (common operation)

[0187] [ka] A flask was charged with 5-mercapto-1-(4-methoxyphenyl)-1H-tetrazole, triphenylphosphine (PPh3; 1.2 equiv.), alcohol (1.2 equiv.), and dry tetrahydrofuran (THF; 4 mL per 1 mmol of aryl thiol compound) under argon. To this mixture, bis(2-methoxyethyl) azodicarboxylate (1.2 equiv.) was slowly added at 0 °C. The mixture was stirred at room temperature for 24 h, and the organic solvent was evaporated under reduced pressure. The residue was purified by column chromatography (ethyl acetate / hexane) to give the sulfide compound. The resulting sulfide compound was dissolved in CHCl (1 mL per 1 mmol of aryl thiol compound). To this solution, a solution of metachloroperbenzoic acid (mCPBA; >65%, 2.5 equiv.) in CHCl (3 mL per 1 mmol of aryl thiol compound) was slowly added at 0 °C, and the mixture was stirred at room temperature for 16 h. The mixture was quenched with saturated Na2SO3 solution and washed with saturated aqueous NaHCO3 (3 times). The organic layer was dried over Na2SO4, filtered, and evaporated under reduced pressure. The residue was purified by column chromatography to give the corresponding secondary alkyl sulfone compound.

[0188] (Synthesis Example 2-13) 4-((1'-anisyl-1H-tetrazol-5'-yl)sulfonyl)tetrahydropyran

[0189] [ka] The product was purified by column chromatography (ethyl acetate:hexane = 1:2) to give the desired product as a white solid (1.77 g, 55% isolated yield, 10 mmol scale). 1 H NMR (400 MHz, CDCl3) δ 1.97-2.07 (m, 2H), 2.14-2.19 (m, 2H), 3.51 (dt, J = 1.6, 12.8 Hz, 2H), 3.90 (s, 3H), 4.13 (m, 3H), 7.07 (dm, J= 8.8 Hz, 2H), 7.58 (dm, J = 8.8 Hz, 2H). 13 C NMR (150 MHz, CDCl3) δ 24.6, 55.7, 61.0, 66.1, 114.7, 125.5, 126.6, 152.3, 161.7. HRMS (ESI) m / z calcd for C 13 H 16 O4N4NaS [M+Na] + : 347.0784, found 347.0786.

[0190] (Synthesis Example 2-14) 4-((1'-anisyl-1H-tetrazol-5'-yl)sulfonyl)-1-(benzyloxycarbonyl)piperidine

[0191] [ka] The product was purified by column chromatography (ethyl acetate:hexane = 1:2) to give the target compound as a white solid (2.51 g, 51% isolated yield, 10.7 mmol scale). 1 H NMR (600 MHz, CDCl3) δ 1.87 (dq, J = 4.2, 12.6 Hz, 2H), 2.25 (d, J = 12.0 Hz, 2H), 2.95 (brs, 2H), 3.89 (s, 3H), 4.03 (tt, J = 4.2, 12.6 Hz, 1H), 4.35 (brs, 1H), 4.42 (brs, 1H), 5.14 (s, 2H), 7.06 (dm, J= 9.0 Hz, 2H), 7.31-7.38 (m, 5H), 7.56 (dm, J = 9.0 Hz, 2H). 13C NMR (150 MHz, CDCl3) δ 24.1, 42.4, 55.7, 61.9, 67.5, 114.7, 125.4, 126.6, 128.0, 128.2, 128.5, 136.2, 152.3, 154.8, 161.7. HRMS (ESI) m / z calcd for C 21 H 23 O5N5NaS [M+Na] + : 480.1312, found 480.1311.

[0192] (Synthesis Example 2-15) 1-p-anisyl-5-((2',3'-dihydro-1H-inden-2'-yl)sulfonyl)-1H-tetrazole

[0193] [ka] The product was purified by column chromatography (ethyl acetate:hexane = 1:5) to give the target compound as a white solid (1.51 g, 61% isolated yield, 7 mmol scale). 1 H NMR (600 MHz, CDCl3) δ 3.54-3.63 (m, 4H), 3.88 (s, 3H), 4.18 (quint, J = 9.0 Hz, 1H), 7.06 (dm, J = 9.0 Hz, 2H), 7.20-7.24 (m, 4H), 7.61 (dm, J = 9.0 Hz, 2H). 13 C NMR (150 MHz, CDCl3) δ 33.3, 55.7, 63.3, 114.7, 124.5, 125.6, 126.6, 127.5, 138.6, 153.1. HRMS (ESI) m / z calcd for C 17 H 16 O3N4NaS [M+Na] + : 379.0835, found 379.0837.

[0194] (Synthesis Example 2-16) 3α-((1'-anisyl-1H-tetrazol-5'-yl)sulfonyl)-5α-androstan-17-one

[0195] [ka] The product was purified by column chromatography (ethyl acetate: CH2Cl2 = 1:50 - 1:30) to give the desired product as a white solid (1.46 g, 27% isolated yield, 11 mmol scale). 1 H NMR (400 MHz, CDCl3) δ 0.78 (dd, J = 3.2, 11.4 Hz, 1H), 0.84 (s, 3H), 0.85 (s, 3H), 0.97 (ddd, J = 3.2, 11.4, 25.2 Hz, 1H), 1.16-1.93 (m, 15H), 2.06 (m, 2H), 2.14 (d, J = 15.6 Hz, 1H), 2.31 (d, J = 15.6 Hz, 1H), 2.42 (dd, J = 8.7, 19.5 Hz, 1H), 3.89 (s, 3H), 4.21 (t, J = 6.0 Hz, 1H), 7.06 (dm, J = 9.0 Hz, 2H), 7.58 (dm, J = 9.0 Hz, 2H). 13 C NMR (150 MHz, CDCl3) δ 11.1, 13.7, 19.8, 20.1, 21.6, 25.9, 27.9, 30.1, 31.2, 33.1, 34.7, 35.4, 35.6, 40.6, 47.6, 51.1, 53.6, 55.6, 59.6, 114.5, 125.6, 126.6, 153.1, 161.5, 221.0. HRMS (ESI) m / zcalcd for C 27 H 36 O4N4NaS [M+Na] + : 535.2349, found 535.2346.

[0196] Synthesis Examples 2-17 to 2-30: Tertiary alkyl sulfone compounds (common operation)

[0197] [ka] A two-neck Schlenk flask equipped with a magnetic stir bar was flame-dried under vacuum, cooled to room temperature, and then backfilled with argon. The flask was charged with the sulfone compound and dry tetrahydrofuran (THF; 5 mL per 1 mmol of sulfone compound). A solution of lithium bis(trimethylsilyl)amide (LiHMDS) (1.3 M in THF, 1.5 equivalents (mono-alkylation) or 3 equivalents (di-alkylation)) was added dropwise to the reaction mixture at −78 °C under argon. After stirring the mixture for 30 min, an alkyl halide (2 equivalents (mono-alkylation) or 4 equivalents (di-alkylation)) was added and stirred at room temperature for 16 h. Saturated aqueous NH4Cl was added to the reaction mixture, and the layers were separated. The aqueous layer was extracted with ethyl acetate (three times), and the combined organic layer was washed with saturated aqueous NaHCO3 and brine. The organic layer was dried over Na2SO4, filtered, and the solvent was evaporated under reduced pressure. The residue was purified by column chromatography to give the corresponding tertiary alkyl sulfone compound.

[0198] (Synthesis Example 2-17) 5-((1',1'-dimethylpropyl)sulfonyl)-1-phenyl-1H-tetrazole

[0199] [ka] The product was purified by column chromatography (ethyl acetate:hexane = 1:10) to give the target compound as a white solid (5.02 g, 90% isolated yield, 20.4 mmol scale). 1 H NMR (600 MHz, CDCl3) δ 0.99 (t, J = 7.2 Hz, 3H), 1.48 (s, 6H), 1.93 (q, J = 7.2 Hz, 2H), 7.52-7.64 (m, 5H). 13C NMR (150 MHz, CDCl3) δ 7.9, 19.6, 27.4, 67.9, 126.1, 129.2, 131.3, 133.3, 151.9. HRMS (ESI) m / z calcd for C 12 H 16 O2N4NaS [M+Na] + : 303.0886, found 303.0888.

[0200] (Synthesis Example 2-18) 5-((1',1'-dimethylpropyl)sulfonyl)-(p-trifluoromethylphenyl)-1H-tetrazole

[0201] [ka] The product was purified by column chromatography (ethyl acetate:hexane = 1:8) to give the desired product as a white foam (791 mg, 91% isolated yield, 2.5 mmol scale). 1 H NMR (400 MHz, CDCl3) δ 1.02 (t, J = 7.6 Hz, 3H), 1.52 (s, 6H), 1.97 (q, J = 7.6 Hz, 2H), 7.77 (d, J = 8.4 Hz, 2H), 7.87 (d, J = 8.4 Hz, 2H). 13 C NMR (150 MHz, CDCl3) δ 7.9, 19.6, 27.4, 68.4, 123.1 (q, J = 271 Hz), 126.6 (q, J = 2.9 Hz), 126.7, 133.4 (q, J = 33.0 Hz), 136.1, 152.1. 19 F NMR (376 MHz, CDCl3) δ -62.8. HRMS (ESI) m / z calcd for C 13 H 15 O2N4F3NaS [M+Na] + : 371.0760, found 371.0760.

[0202] (Synthesis Example 2-19) 1-p-anisyl-5-((1',1'-dimethylpropyl)sulfonyl)-1H-tetrazole

[0203] [ka] The product was purified by column chromatography (ethyl acetate:hexane = 1:6) to obtain the target compound as a pale yellow solid (5.04 g, 85% isolated yield, 20 mmol scale). 1 H NMR (400 MHz, CDCl3) δ 1.00 (t, J = 7.2 Hz, 3H), 1.48 (s, 6H), 1.93 (q, J = 7.2 Hz, 2H), 3.89 (s, 3H), 7.05 (dm, J = 9.2 Hz, 2H), 7.48 (dm, J = 9.2 Hz, 2H). 13 C NMR (150 MHz, CDCl3) δ 7.9, 19.6, 27.4, 55.6, 67.8, 114.3, 125.8, 127.5, 151.9, 161.5. HRMS (ESI) m / z calcd for C 13 H 19 O3N4S [M+H] + : 311.1172, found 311.1173.

[0204] (Synthesis Example 2-20) 2-((1',1'-dimethylpropyl)sulfonyl)benzothiazole

[0205] [ka] The product was purified by column chromatography (ethyl acetate:hexane = 1:10) and GPC to obtain the target compound as a pale yellow solid (360 mg, 27% isolated yield, 5 mmol scale). 1H NMR (600 MHz, CDCl3) δ 1.01 (t, J = 7.6 Hz, 3H), 1.49 (s, 6H), 1.96 (q, J = 7.6 Hz, 2H), 7.59 (dt, J = 1.8, 7.8 Hz, 1H), 7.63 (dt, J = 1.8, 8.4 Hz, 1H), 8.02 (d, J = 7.8 Hz, 1H), 8.25 (d, J = 8.4 Hz, 1H). 13 C NMR (150 MHz, CDCl3) δ 7.9, 20.0, 27.8, 65.4, 122.0, 125.4, 127.4, 127.8, 137.1, 152.9, 163.9. HRMS (ESI) m / zcalcd for C 12 H 16 O2NS2[M+H] + : 270.0617, found 270.0618.

[0206] (Synthesis Example 2-21) 2-((1',1'-dimethylpropyl)sulfonyl)pyridine

[0207] [ka] The product was purified by column chromatography (ethyl acetate:hexane = 1:3) to give the target compound as a pale yellow solid (799 mg, 86% isolated yield, 4.4 mmol scale). 1 H NMR (400 MHz, CDCl3) δ 0.97 (t, J = 7.6 Hz, 3H), 1.38 (s, 6H), 1.84 (q, J = 7.6 Hz, 2H), 7.56 (ddd, J = 0.8, 4.8, 7.6 Hz, 1H), 7.96 (dt, J = 1.6, 7.6 Hz, 1H), 8.10 (d, J = 7.6 Hz, 1H), 8.81 (dd, J = 0.8, 4.8 Hz, 1H). 13C NMR (150 MHz, CDCl3) δ 8.0, 20.1, 27.9, 63.8, 125.4, 127.1, 137.6, 150.0, 155.3. HRMS (ESI) m / z calcd for C 10 H 15 O2NNaS [M+Na] + : 236.0716, found 236.0716.

[0208] (Synthesis Example 2-22) 1-p-anisyl-5-(tert-butylsulfonyl)-1H-tetrazole

[0209] [ka] The product was purified by column chromatography (ethyl acetate:hexane = 1:6) to give the desired product as a white solid (2.43 g, 81% isolated yield, 10 mmol scale). 1 H NMR (600 MHz, CDCl3) δ 1.55 (s, 9H), 3.89 (s, 3H), 7.05 (dm, J= 9.0 Hz, 2H), 7.49 (dm, J = 9.0 Hz, 2H). 13 C NMR (150 MHz, CDCl3) δ 23.2, 55.7, 64.4, 114.4, 125.9, 127.4, 151.8, 161.6. HRMS (ESI) m / z calcd for C 12 H 17 O3N4S [M+H] + : 297.1016, found 297.1018.

[0210] (Synthesis Example 2-23) 1-p-anisyl-5-((1',1'-dimethyl-3'-phenylpropyl)sulfonyl)-1H-tetrazole

[0211] [ka] The product was purified by column chromatography (ethyl acetate:hexane:CH2Cl2=1:8:1-1:2:1) to obtain the target compound as a pale yellow solid (1.80 g, 93% isolated yield, 5 mmol scale). 1 H NMR (600 MHz, CDCl3) δ 1.58 (s, 6H), 2.12-2.15 (m, 2H), 2.68-2.71 (m, 2H), 3.87 (s, 3H), 7.00 (dm, J = 9.0 Hz, 2H), 7.14 (d, J = 7.2 Hz, 2H), 7.21 (t, J = 7.2 Hz,1H), 7.28 (t, J = 7.2 Hz, 2H), 7.43 (dm, J = 9.0 Hz, 2H). 13 C NMR (150 MHz, CDCl3) δ 20.3, 30.0, 36.8, 55.6, 67.5, 114.3, 125.8, 126.4, 127.5, 128.2, 128.6, 140.3, 151.8, 161.5. HRMS (ESI) m / z calcd for C 19 H 22 O3N4NaS [M+Na] + : 409.1305, found 409.1305.

[0212] (Synthesis Example 2-24) 1-p-anisyl-5-(((3'-tert-butyldimethylsilyl)oxy-1',1'-dimethylpropyl)sulfonyl)-1H-tetrazole

[0213] [ka] The product was purified by column chromatography (ethyl acetate:hexane = 1:8) to give the target compound as a white solid (1.72 g, 76% isolated yield, 5.1 mmol scale). 1H NMR (600 MHz, CDCl3) δ 0.04 (s, 6H), 0.87 (s, 9H), 1.56 (s, 6H), 2.13 (t, J = 6.0 Hz, 2H), 3.80 (t, J = 6.0 Hz, 2H), 3.889 (s, 3H), 7.05 (dm, J = 8.4 Hz, 2H), 7.48 (dm, J = 8.4 Hz, 2H). 13 C NMR (150 MHz, CDCl3) δ -5.6, 18.0, 20.6, 25.8, 36.4, 55.6, 58.6, 67.2, 114.3, 125.8, 127.5, 151.8, 161.6. HRMS (ESI) m / z calcd for C 19 H 33 O4N4SSi [M+H] + : 441.1986, found 441.1988.

[0214] (Synthesis Example 2-25) 4-((1'-anisyl-1H-tetrazol-5'-yl)sulfonyl)-4-methyltetrahydropyran

[0215] [ka] Purification was achieved by precipitation with CH2Cl2 and hexane to give the desired product as a pale yellow solid (900 mg, 86% isolated yield, 3 mmol scale). 1 H NMR (400 MHz, CDCl3) δ 1.68 (s, 3H), 1.79 (dd, J = 2.0, 13.2 Hz, 2H), 2.37 (dt, J = 5.2, 13.2, Hz, 2H), 3.57 (dt, J = 2.0, 11.8 Hz, 2H), 3.90 (s, 3H), 3.99 (ddd, J = 2.0, 5.2, 11.8 Hz, 2H), 7.06 (dm, J = 9.2 Hz, 2H), 7.50 (dm, J = 9.2 Hz, 2H). 13C NMR (150 MHz, CDCl3) δ 16.9, 29.3, 55.7, 62.7, 65.4, 114.4, 125.7, 127.4, 151.4, 161.6. HRMS (ESI) m / zcalcd for C 14 H 18 O4N4NaS [M+Na] + : 361.0941, found 361.0941.

[0216] (Synthesis Example 2-26) 4-((1'-anisyl-1H-tetrazol-5'-yl)sulfonyl)-1-benzyloxycarbonyl-4-methylpiperidine

[0217] [ka] The product was purified by column chromatography (ethyl acetate:hexane = 1:4 - 1:1) to give the desired product as a white solid (1.30 g, 93% isolated yield, 3 mmol scale). 1 H NMR (400 MHz, CDCl3) δ 1.63 (s, 3H), 1.90 (d, J = 13.2 Hz, 2H), 2.25 (brs, 2H), 3.05 (brs, 2H), 3.89 (s, 3H), 4.19 (brs, 2H), 5.13 (s, 2H), 7.05 (dm, J = 9.2 Hz, 2H), 7.33-7.39 (m, 5H), 7.48 (dm, J = 9.2 Hz, 2H). 13 C NMR (150 MHz, CDCl3) δ 16.8, 28.9, 39.1, 55.7, 66.1, 67.5, 114.4, 125.6, 127.4, 128.0, 128.2, 128.5, 136.3, 151.4, 154.8, 161.7. HRMS (ESI) m / z calcd for C 22 H 25 O5N5NaS [M+Na] + : 494.1469, found 494.1471.

[0218] (Synthesis Example 2-27) 1-p-anisyl-5-((2'-methylindan-2'-yl)sulfonyl)-1H-tetrazole

[0219] [ka] The product was purified by column chromatography (ethyl acetate:hexane:CH2Cl2=1:8:1-1:6:1) to give the desired product as a yellow solid (1.52 g, 92% isolated yield, 4.5 mmol scale). 1 H NMR (600 MHz, CDCl3) δ 1.75 (s, 3H), 3.15 (d, J = 16.2 Hz, 2H), 3.88 (s, 3H), 3.93 (d, J = 16.2 Hz, 2H), 7.06 (dm, J = 9.0 Hz, 2H), 7.21 (s, 4H), 7.54 (dm, J = 9.0 Hz, 2H). 13 C NMR (150 MHz, CDCl3) δ 22.4, 41.3, 55.6, 71.9, 114.4, 124.7, 125.7, 127.2, 127.5, 138.1, 152.0, 161.6. HRMS (ESI) m / zcalcd for C 18 H 18 O3N4NaS [M+Na] + : 393.0992, found 393.0991.

[0220] (Synthesis Example 2-28) 1-p-anisyl-5-((1',1'-diethylpropyl)sulfonyl)-1H-tetrazole

[0221] [ka] The product was purified by column chromatography (ethyl acetate:hexane = 1:7 - 1:6) to give the target compound as a colorless viscous liquid (393 mg, 58% isolated yield, 1.0 mmol scale). 1 H NMR (600 MHz, CDCl3) δ 0.95 (t, J = 7.5 Hz, 9H), 1.92 (q, J= 7.5 Hz, 6H), 3.89 (s, 3H), 7.05 (dm, J = 9.0 Hz, 2H), 7.47 (dm, J= 9.0 Hz, 2H). 13 C NMR (150 MHz, CDCl3) δ 8.0, 24.4, 55.6, 73.9, 114.2, 125.8, 127.7, 152.6, 161.5. HRMS (ESI) m / z calcd for C 15 H 22 O3N4NaS [M+Na] + : 361.1305, found 361.1305.

[0222] (Synthesis Example 2-29) 1-p-anisyl-5-(1'-(N,N-dimethylaminopropyl)sulfonyl)-1H-tetrazole

[0223] [ka] Dimethylcarbamoyl chloride was used. Purification was carried out by column chromatography (ethyl acetate:hexane = 1:2). The target product was obtained as a white solid (610 mg, 98% isolated yield, 1.8 mmol scale). 1 H NMR (600 MHz, CDCl3) δ 1.01 (t, J = 7.2 Hz, 3H), 2.26 (quin, J = 7.2 Hz, 2H), 2.93 (s, 3H), 3.15 (s, 3H), 3.87 (s, 3H), 4.82 (t, J= 7.2 Hz, 1H), 7.02 (dm, J = 9.0 Hz, 2H), 7.52 (dm, J = 9.0 Hz, 2H). 13C NMR (150 MHz, CDCl3) δ 10.9, 21.7, 36.1, 38.0, 55.5, 68.4, 114.0, 125.6, 127.4, 152.3, 161.4, 163.1. HRMS (ESI) m / zcalcd for C 14 H 20 O4N5S [M+H] + : 354.1231, found 354.1230.

[0224] (Synthesis Example 2-30) 1-p-anisyl-5-(1'-(diethylphosphorylpropyl)sulfonyl)-1H-tetrazole

[0225] [ka] Diethyl chlorophosphite was used. Purification was carried out by column chromatography (ethyl acetate:hexane = 2:1). The target product was obtained as a yellow solid (740 mg, 51% isolated yield, 3.5 mmol scale). 1 H NMR (400 MHz, CDCl3) δ 1.26 (t, J =7.2 Hz, 3H), 1.27 (t, J= 7.2 Hz, 3H), 1.30 (t, J = 7.2 Hz, 3H), 2.16 (dquin, J = 7.2 Hz, 1H), 2.35 (m, 1H), 3.88 (s, 3H), 4.11 (m, 4H), 4.25 (ddd, J = 4.8, 7.2, 17.6 Hz, 1H), 7.03 (dm, J = 9.2 Hz, 2H), 7.58 (dm, J = 9.2 Hz, 2H). 13 C NMR (150 MHz, CDCl3) δ 12.6 (d, J= 2.9 Hz), 16.2 (dd, J = 2.9, 5.7 Hz), 17.9 (d, J = 2.9 Hz), 55.6, 63.4 (d, J = 5.7 Hz), 64.0, 64.2 (d, J = 5.7 Hz), 65.0, 114.2, 125.7. 31P NMR (160 MHz, CDCl3) δ 14.4. HRMS (ESI) m / z calcd for C 15 H 24 O6N4PS [M+H] + : 419.1149, found 419.1149.

[0226] Synthesis Example 2-31: 1-p-anisyl-5-((1',1'-dimethyl-3'-hydroxypropyl)sulfonyl)-1H-tetrazole

[0227] [ka] A 300 mL flask was charged with 1-p-anisyl-5-((3'-tert-butyldimethylsilyl)oxy-1',1'-dimethylpropyl)sulfonyl)-1H-tetrazole (Synthesis Example 2-24; 4.40 g, 10.0 mmol), tetrahydrofuran (THF; 50 mL), and HO (25 mL). To this mixture was added 1N aqueous HCl (13 mL) at room temperature. After stirring at room temperature for 4 hours, brine was added and the mixture was extracted with ethyl acetate (3 times). The organic layer was dried over NaSO, filtered, and the solvent was evaporated under reduced pressure. The residue was purified by column chromatography (ethyl acetate / hexane = 1:2) to give 1-p-anisyl-5-((1',1'-dimethyl-3'-hydroxypropyl)sulfonyl)-1H-tetrazole (3.01 g, 92%) as a white solid. 1 H NMR (600 MHz, CDCl3) δ 1.58 (s, 6H), 1.64 (t, J = 5.7 Hz, 1H), 2.21 (t, J= 5.7 Hz, 2H), 3.85 (q, J = 5.7 Hz, 2H), 3.89 (s, 3H), 7.05 (dm, J= 9.0 Hz, 2H), 7.49 (dm, J = 9.0 Hz, 2H). 13 C NMR (150 MHz, CDCl3) δ 21.0, 37.3, 55.7, 58.3, 67.0, 114.4, 125.8, 127.5, 151.8, 161.6. HRMS (ESI) m / z calcd for C 13H 19 O4N4S [M+H] + : 327.1122, found 327.1122.

[0228] Synthesis Example 2-32: 1-p-anisyl-5-((3'-cyano-1',1'-dimethylpropyl)sulfonyl)-1H-tetrazole

[0229] [ka] A 30 mL flask was charged with 1-p-anisyl-5-((1',1'-dimethyl-3'-hydroxypropyl)sulfonyl)-1H-tetrazole (Synthesis Example 2-31; 330 mg, 1.0 mmol), triphenylphosphine (PPh; 660 mg, 2.5 mmol), acetone cyanohydrin (0.23 mL, 2.5 mmol), and tetrahydrofuran (THF; 5.0 mL). To this mixture was added bis(2-methoxyethyl) azodicarboxylate (DMEAD; 0.59 g, 2.5 mmol) at 0°C and stirred at room temperature for 16 hours. Brine was added to the mixture, which was then extracted with ethyl acetate (3 times). The organic layer was dried over Na2SO4, filtered, and the solvent was evaporated under reduced pressure. The residue was purified by column chromatography (ethyl acetate:hexane=1:4) to give 1-p-anisyl-5-((3′-cyano-1′,1′-dimethylpropyl)sulfonyl)-1H-tetrazole (190 mg, 55%) as a yellow solid. 1 H NMR (600 MHz, CDCl3) δ 1.54 (s, 6H), 2.35-2.38 (m, 2H), 2.58-2.61 (m, 2H), 3.90 (s, 3H), 7.06 (dm, J = 8.4 Hz, 2H), 7.49 (dm, J = 8.4 Hz, 2H). 13 C NMR (150 MHz, CDCl3) δ 12.5, 20.4, 31.2, 55.6, 66.0, 114.4, 118.6, 125.4, 127.4, 151.3, 161.6. HRMS (ESI) m / z calcd for C 14 H 18 O3N5S [M+H]+ : 336.1125, found 336.1123.

[0230] Synthesis Example 2-33: 1-p-anisyl-5-((3'-bromo-1',1'-dimethylpropyl)sulfonyl)-1H-tetrazole

[0231] [ka] A 50 mL flask was charged with 5-((1',1'-dimethyl-3'-hydroxypropyl)sulfonyl)-1-p-anisyl-1H-tetrazole (Synthesis Example 2-31; 980 mg, 3.0 mmol), tetrabromomethane (1.49 g, 4.5 mmol), and CHCl (15 mL). Triphenylphosphine (PPh; 1.18 g, 4.5 mmol) was added to this mixture at 0°C, and the mixture was stirred at room temperature for 16 hours. After stirring, the mixture was evaporated under reduced pressure. The residue was purified by column chromatography (ethyl acetate:hexane = 1:8) to give 1-p-anisyl-5-((3'-bromo-1',1'-dimethylpropyl)sulfonyl)-1H-tetrazole. 1 H NMR (600 MHz, CDCl3) δ 1.56 (s, 6H), 2.49-2.52 (m, 2H), 3.44-3.47 (m, 2H), 3.90 (s, 3H), 7.06 (dm, J = 9.0 Hz, 2H), 7.49 (dm, J = 9.0 Hz, 2H). 13 C NMR (150 MHz, CDCl3) δ 20.7, 25.6, 38.7, 55.7, 67.4, 114.4, 125.6, 127.4, 151.5, 161.7. HRMS (ESI) m / zcalcd for C 13 H 17 O3N4BrNaS [M+Na] + : 411.0097, found 411.0098.

[0232] Synthesis Example 2-34: 1-[3-((1'-anisyl-1H-tetrazol-5'-yl)sulfonyl)-3,3-dimethyl]propyl 1'-tert-butyl-N-(tert-butoxycarbonyl)-L-glutamate

[0233] [ka] Under an argon atmosphere, 1-p-anisyl-5-((1',1'-dimethyl-3'-hydroxypropyl)sulfonyl)-1H-tetrazole (Synthesis Example 2-31; 979 mg, 3 mmol), 1-tert-butyl-N-(tert-butoxycarbonyl)-L-glutamate (1.09 g, 3.6 mmol), 4-dimethylaminopyridine (513 mg, 4.2 mmol), and dry CHCl (10 mL) were added to a flask. 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide (760 μL, 4.2 mmol) was added to this mixture at room temperature. The mixture was stirred at room temperature for 16 hours and then passed through a pad of silica gel, washing successively with ethyl acetate (approximately 20 mL). The filtrate was concentrated under reduced pressure. The residue was purified by column chromatography to give 1-[3-((1′-anisyl-1H-tetrazol-5′-yl)sulfonyl)-3,3-dimethyl]propyl 1′-tert-butyl-N-(tert-butoxycarbonyl)-L-glutamate (1.70 g, 92%) as a beige solid. 1 H NMR (600 MHz, CDCl3) δ 1.44 (s, 9H), 1.47 (s, 9H), 1.55 (s, 6H), 1.88 (m, 1H), 2.15 (m, 1H), 2.39 (t, J= 6.9 Hz, 2H), 2.30-2.44 (m, 2H), 3.90 (s, 3H), 4.18-4.21 (m, 1H), 4.23-4.29 (m, 2H), 5.15 (d, J = 6.9 Hz, 1H), 7.06 (dm, J = 9.0 Hz, 2H), 7.50 (dm, J = 9.0 Hz, 2H). 13 C NMR (150 MHz, CDCl3) δ 20.49, 20.54, 27.8, 28.1, 30.0, 33.3, 53.1, 55.5, 59.7, 66.3, 79.6, 82.1, 114.3, 125.6, 127.4, 151.5, 155.2, 161.5, 171.1, 172.2. HRMS (ESI) m / z calcd for C 27 H41 ON5NaS [M+Na] + : 634.2517, found 634.2520.

[0234] Example 1: Synthesis of alkyl-substituted polycyclic aromatic compounds (common operation)

[0235] [ka] A 10 mL sealable glass vessel containing a magnetic stir bar was flame dried under vacuum, cooled to room temperature, and then backfilled with argon. The polycyclic aromatic compound (0.2 mmol), alkyl sulfone compound (0.6 mmol), zinc acetate (Zn(OAc)2; 110.1 mg, 0.6 mmol), and Na2CO3 (63.6 mg, 0.6 mmol) were added to the glass vessel. The mixture was evaporated under vacuum and refilled with argon. This cycle was repeated two more times. Under an argon atmosphere, dimethyl sulfoxide (DMSO; 1.0 mL) was added to the reaction mixture, the glass vessel was sealed, and the mixture was stirred at approximately 30–35 °C under blue light irradiation at 456 nm. The mixture was passed through a pad of silica gel, washed successively with ethyl acetate and hexane, and the filtrate was concentrated under reduced pressure. The residue was purified by gel permeation chromatography (GPC), post-transcriptional liquid chromatography (PTLC), or column chromatography.

[0236] Unless otherwise stated, alkyl sulfone compounds were synthesized according to typical procedures. All products were purified by column chromatography, PTLC, or GPC (preparative recycling HPLC equipped with a JAIGEL-1H / JAIGEL-2H column (eluent: ethyl acetate or CHCl3)).

[0237] Example 1-1 Using 2-tert-butylpyrene as the substrate and the alkylsulfone compound obtained in Synthesis Example 2-19 as the reactant, the reaction was carried out for 24 hours and purified by GPC.

[0238] (1) 2-tert-butyl-6-(1',1'-dimethylpropyl)pyrene

[0239] [ka] The target product was obtained as a pale yellow solid (20.6 mg, 31% isolated yield, 0.2 mmol scale). 1 H NMR (400 MHz, CDCl3) δ 0.64 (t, J = 7.6 Hz, 3H), 1.57 (s, 9H), 1.72 (s, 6H), 2.26 (q, J = 7.6 Hz, 2H), 7.98 (s, 2H), 8.00 (d, J = 8.0 Hz, 1H), 8.03 (d, J = 9.6 Hz, 1H), 8.07 (d, J = 8.0 Hz, 1H), 8.17 (d, J = 9.2 Hz, 1H), 8.18 (d, J= 9.2 Hz, 1H), 8.68 (d, J = 9.6 Hz, 1H). 13 C NMR (150 MHz, CDCl3) δ 9.7, 30.5, 31.9, 35.1, 35.7, 40.2, 121.7, 122.1, 123.5, 124.4, 125.0, 125.8, 125.89, 125.95, 126.9, 127.3, 128.8, 129.7, 130.1, 131.4, 142.6, 148.7. HRMS (DART) m / z calcd for C 25 H 29 [M+H] + : 329.2269, found 329.2270.

[0240] (2) 2-tert-butyl-6,8-bis(1',1'-dimethylpropyl)pyrene

[0241] [ka] The target product was obtained as a pale yellow solid (21.9 mg, 27% isolated yield, 0.2 mmol scale). 1 H NMR (400 MHz, CDCl3) δ 0.64 (t, J = 7.6 Hz, 6H), 1.56 (s, 9H), 1.73 (s, 12H), 2.24 (q, J = 7.6 Hz, 4H), 7.96 (d, J = 9.6 Hz, 2H), 8.07 (s, 1H), 8.13 (s, 2H), 8.64 (d, J= 9.6 Hz, 2H). 13 C NMR (150 MHz, CDCl3) δ 9.6, 30.5, 31.8, 35.0, 35.8, 40.5, 121.7, 124.1, 125.1, 125.2, 125.6, 127.35, 127.41, 130.5, 141.2, 148.4. HRMS (DART) m / z calcd for C 30 H 39 [M+H] + : 399.3052, found 399.3047.

[0242] Example 1-2 Using 2-tert-butylpyrene as the substrate and the alkylsulfone compound obtained in Synthesis Example 2-22 as the reactant, the reaction was carried out for 24 hours, and the product was purified by GPC.

[0243] (1) 1,7-di-tert-butylpyrene

[0244] [ka] The target product was obtained as a pale yellow solid (8.0 mg, 13% isolated yield, 0.2 mmol scale). 1 H NMR (400 MHz, CDCl3) δ 1.59 (s, 9H), 1.78 (s, 9H), 7.98 (s, 2H), 8.05-8.09 (m, 3H), 8.17 (d, J = 7.6 Hz, 1H), 8.18 (d, J = 7.6 Hz, 1H), 8.71 (d, J = 9.6 Hz, 1H). 13C NMR (150 MHz, CDCl3) δ 31.9, 32.4, 35.1, 36.4, 121.8, 122.2, 123.46, 123.51, 124.5, 125.9, 126.0, 126.1, 126.9, 127.3, 128.5, 129.8, 130.0, 131.3, 144.2, 148.8. HRMS (DART) m / z calcd for C 24 H 27 [M+H] + : 315.2113, found 315.2114.

[0245] (2) 1,3,7-tri-tert-butylpyrene

[0246] [ka] The target product was obtained as a pale yellow solid (28.3 mg, 36% isolated yield, 0.2 mmol scale). 1 H NMR (400 MHz, CDCl3) δ 1.56 (s, 9H), 1.79 (s, 18H), 7.98 (d, J = 9.6 Hz, 2H), 8.13 (s, 2H), 8.21 (s, 1H), 8.66 (d, J = 9.6 Hz, 2H). 13 C NMR (150 MHz, CDCl3) δ 31.9, 32.4, 35.0, 36.8, 121.8, 122.1, 124.1, 125.3, 125.9, 127.2, 127.6, 130.5, 143.0, 148.5. HRMS (DART) m / z calcd for C 28 H 35 [M+H] + : 371.2739, found 371.2738.

[0247] Examples 1-3 The compound obtained in Synthesis Example 1-1 was used as the substrate, and the alkyl sulfone compound obtained in Synthesis Example 2-19 was used as the reactant, and the reaction was carried out for 30 hours, followed by purification by GPC.

[0248] (1) 6-(1',1'-dimethylpropyl)-2-mesitylpyrene

[0249] [ka] The target product was obtained as a pale yellow amorphous solid (21.3 mg, 23% isolated yield, 0.2 mmol scale). 1 H NMR (400 MHz, CDCl3) δ 0.67 (t, J = 7.6 Hz, 3H), 1.74 (s, 6H), 2.03 (s, 6H), 2.28 (q, J = 7.6 Hz, 2H), 2.39 (s, 3H), 7.03 (s, 2H), 7.94 (d, J = 8.0 Hz, 2H), 7.98 (d, J = 9.2 Hz, 1H), 8.03-8.08 (m, 3H), 8.12 (d, J = 8.0 Hz, 1H), 8.75 (d, J = 9.6 Hz, 1H). 13 C NMR (150 MHz, CDCl3) δ 9.7, 21.0, 21.1, 30.6, 35.7, 40.3, 124.1, 124.8, 125.3, 125.4, 125.8, 125.9, 126.0, 126.7, 127.6, 128.1, 128.9, 129.8, 130.4, 131.7, 136.3, 136.8, 138.7, 139.1, 142.9. HRMS (DART) m / z calcd for C 30 H 31 [M+H] + : 391.2426, found 391.2120.

[0250] (2) 6,8-bis(1',1'-dimethylpropyl)-2-mesitylpyrene

[0251] [ka] The target product was obtained as a pale yellow amorphous solid (19.2 mg, 25% isolated yield, 0.2 mmol scale). 1 H NMR (400 MHz, CDCl3) δ 0.67 (t, J = 7.4 Hz, 6H), 1.75 (s, 12H), 2.03 (s, 6H), 2.26 (q, J = 7.4 Hz, 4H), 2.39 (s, 3H), 7.03 (s, 2H), 7.91 (s, 2H), 7.99 (d, J = 9.6 Hz, 2H), 8.12 (s, 1H), 8.70 (d, J = 9.6 Hz, 2H). 13 C NMR (150 MHz, CDCl3) δ 9.7, 21.0, 21.1, 30.6, 35.9, 40.6, 124.7, 125.1, 125.4, 125.5, 125.9, 127.4, 127.5, 128.1, 130.9, 136.3, 136.7, 138.4, 139.1, 141.6. HRMS (DART) m / zcalcd for C 35 H 41 [M+H] + : 461.3208, found 461.3208.

[0252] Examples 1-4 Using 4,4,5,5-tetramethyl-2-(pyren-2-yl)-1,3,2-dioxaborolane as the substrate and the alkylsulfone compound obtained in Synthesis Example 2-19 as the reactant, the reaction was carried out for 30 hours and purified by GPC.

[0253] (1) 6-(1',1'-dimethylpropyl)-2-(4',4',5',5'-tetramethyl-1',3',2'-dioxaborolan-2'-yl)pyrene

[0254] [ka] The desired product was obtained as an orange solid (20.6 mg, 26% isolated yield, 0.2 mmol scale). 1 H NMR (600 MHz, CDCl3) δ 0.66 (t, J = 7.8 Hz, 3H), 1.46 (s, 12H), 1.72 (s, 6H), 2.26 (q, J = 7.8 Hz, 2H), 7.99 (d, J = 9.0 Hz, 1H), 8.03 (d, J = 9.0 Hz, 1H), 8.05 (d, J= 8.4 Hz, 1H), 8.09 (d, J = 8.4 Hz, 1H), 8.59 (s, 1H), 8.60 (s, 1H), 8.69 (d, J = 8.4 Hz, 1H). 13 C NMR (150 MHz, CDCl3) δ 9.7, 25.0, 30.5, 35.7, 40.2, 84.1, 124.5, 125.76, 125.82, 125.9, 126.1, 127.0, 127.1, 127.4, 129.6, 130.4, 130.7, 131.0, 131.1, 142.7. HRMS (ESI) m / z calcd for C 27 H 32 O2B [M+H] + : 399.2490, found 399.2491.

[0255] (2) 6,8-bis(1',1'-dimethylpropyl)-2-(4',4',5',5'-tetramethyl-1',3',2'-dioxaborolan-2'-yl)pyrene

[0256] [ka] The desired product was obtained as an orange amorphous solid (23.0 mg, 25% isolated yield, 0.2 mmol scale). 1H NMR (600 MHz, CDCl3) δ 0.68 (t, J = 7.5 Hz, 6H), 1.46 (s, 12H), 1.74 (s, 12H), 2.25 (q, J = 7.5 Hz, 4H), 8.01 (d, J = 9.6 Hz, 2H), 8.13 (s, 1H), 8.55 (s, 2H), 8.64 (d, J= 9.6 Hz, 2H). 13 C NMR (150 MHz, CDCl3) δ 9.7, 25.0, 30.5, 35.8, 40.6, 84.1, 125.4, 125.6, 125.9, 127.3, 127.6, 128.1, 129.9, 130.8, 141.3. HRMS (ESI) m / z calcd for C 32 H 42 O2B [M+H] + : 469.3272, found 469.3275.

[0257] Examples 1-5 Using 2-triethylsilylpyrene as the substrate and the alkylsulfone compound obtained in Synthesis Example 2-19 as the reactant, the reaction was carried out for 30 hours, and the product was purified by GPC.

[0258] (1) 6-(1',1'-dimethylpropyl)-2-triethylsilylpyrene

[0259] [ka] The desired product was obtained as a pale yellow oil (18.7 mg, 24% isolated yield, 0.2 mmol scale). 1 H NMR (400 MHz, CDCl3) δ 0.64 (t, J = 7.6 Hz, 3H), 0.96-1.08 (m, 15H), 1.73 (s, 6H), 2.26 (q, J = 7.6 Hz, 2H), 8.00 (s, 2H), 8.02-8.10 (m, 3H), 8.25 (d, J = 8.4 Hz, 2H), 8.70 (d, J= 9.6 Hz, 1H).13 C NMR (150 MHz, CDCl3) δ 3.6, 7.5, 9.7, 30.5, 35.7, 40.2, 124.5, 125.5, 125.6, 125.7, 125.90, 125.93, 126.9, 127.3, 129.2, 129.4, 130.0, 130.6, 130.7, 134.7, 142.6. HRMS (DART) m / z calcd for C 27 H 35 Si [M+H] + : 387.2508, found 387.2510.

[0260] (2) 6,8-bis(1',1'-dimethylpropyl)-2-triethylsilylpyrene

[0261] [ka] The target product was obtained as a pale yellow solid (22.3 mg, 24% isolated yield, 0.2 mmol scale). 1 H NMR (600 MHz, CDCl3) δ 0.64 (t, J = 7.8 Hz, 6H), 0.99-1.06 (m, 15H), 1.74 (s, 12H), 2.25 (q, J = 7.8 Hz, 4H), 7.99 (d, J = 9.0 Hz, 2H), 8.10 (s, 1H), 8.22 (s, 2H), 8.66 (d, J= 9.0 Hz, 2H). 13 C NMR (150 MHz, CDCl3) δ 3.6, 7.5, 9.7, 30.5, 35.8, 40.6, 125.2, 125.6, 126.1, 127.4, 127.8, 129.7, 130.5, 134.3, 141.2. HRMS (DART) m / z calcd for C 32 H 45 Si [M+H] + : 457.3291, found 457.3283.

[0262] Examples 1-6 The compound obtained in Synthesis Example 1-2 was used as the substrate, and the alkyl sulfone compound obtained in Synthesis Example 2-19 was used as the reactant. The reaction was carried out for 30 hours, and the product was purified by PTLC (hexane:ethyl acetate=50:1).

[0263] (1) 2-tert-butyl-6-(1',1'-dimethylpropyl)-8-(2'-methyl-1',3'-dioxolan-2-yl)pyrene

[0264] [ka] The desired product was obtained as a yellow solid (51.8 mg, 63% isolated yield, 0.3 mmol scale). 1 H NMR (400 MHz, CDCl3) δ 0.65 (t, J = 7.5 Hz, 3H), 1.57 (s, 9H), 1.74 (s, 6H), 2.03 (s, 3H), 2.25 (q, J = 7.5 Hz, 2H), 3.81-3.85 (m, 2H), 4.15-4.19 (m, 2H), 8.02 (d, J = 9.6 Hz, 2H), 8.17 (s, 2H), 8.35 (s, 1H), 8.66 (d, J = 9.6 Hz, 1H), 8.83 (d, J = 9.6 Hz, 1H). 13 C NMR (150 MHz, CDCl3) δ 9.7, 28.0, 30.6, 31.8, 35.0, 35.7, 40.2, 64.2, 110.4, 122.0, 122.3, 123.1, 123.6, 125.2, 125.6, 126.1, 126.5, 126.7, 127.0, 129.1, 130.2, 130.8, 134.6, 141.7, 148.7. HRMS (ESI) m / z calcd for C 29 H 35 O2 [M+H] + : 415.2632, found 415.2631.

[0265] Examples 1-6 The compound obtained in Synthesis Example 1-2 was used as the substrate, and the alkyl sulfone compound obtained in Synthesis Example 2-23 was used as the reactant. The reaction was carried out for 30 hours, and the product was purified by PTLC (hexane:ethyl acetate=40:1).

[0266] (1) 2-tert-butyl-6-(1',1'-dimethyl-3'-phenylpropyl)-8-(2'-methyl-1',3'-dioxolan-2-yl)pyrene

[0267] [ka] The target product was obtained as a pale yellow amorphous solid (54.9 mg, 56% isolated yield, 0.2 mmol scale). 1 H NMR (600 MHz, CDCl3) δ 1.58 (s, 9H), 1.83 (s, 6H), 2.04 (s, 3H), 2.22-2.25 (m, 2H), 2.52-2.55 (m, 2H), 3.84-3.86 (m, 2H), 4.16-4.18 (m, 2H), 6.97 (d, J = 7.8 Hz, 2H), 7.08 (d, J = 7.8 Hz, 1H), 7.16 (d, J= 7.8 Hz, 2H), 8.05 (d, J = 9.6 Hz, 1H), 8.06 (d, J = 9.6 Hz, 1H), 8.20 (s, 2H), 8.41 (s, 1H), 8.71 (d, J = 9.6 Hz, 1H), 8.85 (d, J = 9.6 Hz, 1H). 13C NMR (150 MHz, CDCl3) δ 28.0, 31.2, 31.8, 32.1, 35.1, 40.2, 46.0, 64.2, 110.3, 122.1, 122.4, 123.0, 123.6, 125.16, 125.25, 125.5, 126.4, 126.6, 126.8, 127.1, 128.17, 128.24, 129.1, 130.3, 130.8, 134.8, 141.0, 142.9, 148.8. 35 H 39 O2 [M+H] + : 491.2945, found 491.2945.

[0268] Examples 1-7 The compound obtained in Synthesis Example 1-2 was used as the substrate, and the alkyl sulfone compound obtained in Synthesis Example 2-24 was used as the reactant. The reaction was carried out for 30 hours, and the product was purified by PTLC (hexane:ethyl acetate=40:1).

[0269] (1) 2-tert-butyl-6-(3'-tert-butyldimethylsilyl)oxy-1',1'-dimethylpropyl)-8-(2'-methyl-1',3'-dioxolan-2-yl)pyrene

[0270] [ka] The target product was obtained as a white amorphous solid (60.6 mg, 57% isolated yield, 0.2 mmol scale). 1H NMR (600 MHz, CDCl3) δ -0.15 (s, 6H), 0.77 (s, 9H), 1.57 (s, 9H), 1.79 (s, 6H), 2.02 (s, 3H), 2.50 (t, J= 7.2 Hz, 2H), 3.42 (t, J = 7.2 Hz, 2H), 3.81-3.83 (m, 2H), 4.15-4.18 (m, 2H), 8.030 (d, J = 9.6 Hz, 1H), 8.034 (d, J = 9.6 Hz, 1H), 8.12 (s, 2H), 8.35 (s, 1H), 8.67 (d, J = 9.6 Hz, 1H), 8.83 (d, J = 9.6 Hz, 1H). 13 C NMR (150 MHz, CDCl3) δ -5.4, 18.1, 25.8, 27.9, 31.4, 31.8, 35.0, 38.8, 45.6, 60.8, 64.2, 110.3, 122.1, 122.4, 122.5, 123.6, 125.1, 125.4, 126.3, 126.6, 126.8, 127.0, 129.0, 130.2, 130.7, 134.7, 141.3, 148.8. HRMS (ESI) m / z calcd for C 35 H 49 O3Si [M+H] + : 545.3445, found 545.3447.

[0271] Examples 1-8 The compound obtained in Synthesis Example 1-2 was used as the substrate, and the alkyl sulfone compound obtained in Synthesis Example 2-32 was used as the reactant. The reaction was carried out for 24 hours, and the product was purified by PTLC (hexane:ethyl acetate=10:1).

[0272] (1) 2-tert-butyl-6-(3'-cyano-1',1'-dimethylpropyl)-8-(2'-methyl-1',3'-dioxolan-2-yl)pyrene

[0273] [ka] The target product was obtained as a pale yellow amorphous solid (25.4 mg, 58% isolated yield, 0.1 mmol scale). 1 H NMR (400 MHz, CDCl3) δ 1.58 (s, 9H), 1.81 (s, 6H), 1.91 (t, J = 8.4 Hz, 2H), 2.01 (s, 3H), 2.65 (q, J = 8.4 Hz, 2H), 3.82-3.86 (m, 2H), 4.16-4.20 (m, 2H), 8.06 (d, J = 9.6 Hz, 1H), 8.09 (d, J = 9.6 Hz, 1H), 8.21 (s, 2H), 8.32 (s, 1H), 8.52 (d, J= 9.6 Hz, 1H), 8.84 (d, J = 9.6 Hz, 1H). 13 C NMR (150 MHz, CDCl3) δ 13.5, 28.0, 30.87, 31.8, 35.1, 38.4, 39.7, 64.3, 110.2, 120.1, 122.5, 122.8, 122.9, 123.5, 124.2, 125.0, 127.0, 127.1, 127.2, 127.3, 128.8, 130.1, 130.7, 135.2, 138.1, 149.1. HRMS (ESI) m / z calcd for C 30 H 33 O2NNa [M+Na] + : 462.2404, found 462.2404.

[0274] Examples 1-9 The compound obtained in Synthesis Example 1-2 was used as the substrate, and the alkyl sulfone compound obtained in Synthesis Example 2-31 was used as the reactant. The reaction was carried out for 30 hours, and the mixture was purified by PTLC (hexane:ethyl acetate=3:1).

[0275] (1) 2-tert-butyl-6-(1',1'-dimethyl-3'-hydroxypropyl)-8-(2'-methyl-1',3'-dioxolan-2-yl)pyrene

[0276] [ka] The target product was obtained as a colorless amorphous solid (49.3 mg, 57% isolated yield, 0.2 mmol scale). 1 H NMR (400 MHz, CDCl3) δ 1.57 (s, 9H), 1.79 (s, 6H), 2.01 (s, 3H), 2.54 (t, J = 7.4 Hz, 2H), 3.41 (t, J = 7.4 Hz, 2H), 3.80-3.83 (m, 2H), 4.14-4.18 (m, 2H), 8.03 (d, J = 9.6 Hz, 1H), 8.04 (d, J = 9.6 Hz, 1H), 8.18 (s, 2H), 8.34 (s, 1H), 8.66 (d, J= 9.6 Hz, 1H), 8.82 (d, J = 9.6 Hz, 1H). 13 C NMR (150 MHz, CDCl3) δ 27.9, 31.4, 31.8, 35.0, 38.6, 45.5, 60.5 ,64.2, 110.3, 122.2, 122.4, 122.5, 123.5, 125.1, 125.2, 126.6, 126.7, 126.9, 127.0, 128.9, 130.2, 130.7, 134.9, 140.7, 148.9. HRMS (ESI) m / z calcd for C 29 H 34 O3Na [M+Na] + : 453.2400, found 453.2402.

[0277] Examples 1-10 The compound obtained in Synthesis Example 1-2 was used as the substrate, and the alkyl sulfone compound obtained in Synthesis Example 2-33 was used as the reactant. The reaction was carried out for 30 hours, and the product was purified by PTLC (hexane:ethyl acetate=50:1).

[0278] (1) 6-(3'-bromo-1',1'-dimethylpropyl)-2-tert-butyl-8-(2'-methyl-1',3'-dioxolan-2-yl)pyrene

[0279] [ka] The target product was obtained as a colorless amorphous solid (40.7 mg, 41% isolated yield, 0.2 mmol scale). 1 H NMR (600 MHz, CDCl3) δ 1.57 (s, 9H), 1.80 (s, 6H), 2.01 (s, 3H), 2.84 (t, J = 8.4 Hz, 2H), 3.00 (t, J = 8.4 Hz, 2H), 3.82-3.84 (m, 2H), 4.16-4.18 (m, 2H), 8.05 (d, J = 9.6 Hz, 1H), 8.08 (d, J = 9.6 Hz, 1H), 8.20 (s, 2H), 8.32 (s, 1H), 8.59 (d, J= 9.6 Hz, 1H), 8.83 (d, J = 9.6 Hz, 1H). 13 C NMR (150 MHz, CDCl3) δ 28.0, 29.5, 31.0, 31.8, 31.9, 35.1, 46.6, 64.2, 110.2, 122.3, 122.6, 122.7, 123.5, 124.6, 125.1, 126.9, 127.0, 127.1, 128.9, 130.1, 130.7, 135.0, 139.1, 149.0. HRMS (ESi) m / z calcd for C 29 H 34 O2Br [M+H] + : 493.1737, found 493.1738.

[0280] Examples 1-11 The compound obtained in Synthesis Example 1-2 was used as the substrate, and the alkyl sulfone compound obtained in Synthesis Example 2-25 was used as the reactant. The reaction was carried out for 30 hours, and the product was purified by column chromatography (hexane:ethyl acetate = 10:1 to 6:1).

[0281] (1) 2-tert-butyl-6-(2'-methyl-1',3'-dioxolan-2-yl)-8-(4'-(4'-methyltetrahydro-2H-pyran)pyrene)

[0282] [ka] The target product was obtained as a colorless amorphous solid (50.1 mg, 57% isolated yield, 0.2 mmol scale). 1 H NMR (600 MHz, CDCl3) δ 1.57 (s, 9H), 1.87 (s, 3H), 2.02 (s, 3H), 2.20-2.23 (m, 2H), 2.62-2.66 (m, 2H), 3.80-3.88 (m, 4H), 3.91-3.95 (m, 2H), 4.15-4.20 (m, 2H), 8.03 (d, J = 9.0 Hz, 1H), 8.05 (d, J = 9.6 Hz, 1H), 8.18-8.19 (m, 2H), 8.37 (s, 1H), 8.61 (d, J = 9.6 Hz, 1H), 8.85 (d, J = 9.0 Hz, 1H). 13 C NMR (150 MHz, CDCl3) δ 27.2, 28.0, 31.8, 35.0, 37.4, 39.5, 64.3, 64.7, 110.3, 122.1, 122.2, 122.5, 123.6, 125.1, 125.2, 126.2, 126.6, 127.0, 127.4, 128.6, 130.1, 130.7, 135.0, 141.2, 148.9. HRMS (ESI) m / z calcd for C 30 H 35 O3 [M+H] + : 443.2581, found 443.2581.

[0283] Examples 1-12 The compound obtained in Synthesis Example 1-2 was used as the substrate, and the alkyl sulfone compound obtained in Synthesis Example 2-27 was used as the reactant. The reaction was carried out for 30 hours, and the product was purified by PTLC (hexane:ethyl acetate=40:1).

[0284] (1) 2-tert-butyl-6-(2'-methyl-1',3'-dioxolan-2-yl)-8-(2'-methylindan-2'-yl)pyrene

[0285] [ka] The target product was obtained as a pale yellow liquid (42.5 mg, 45% isolated yield, 0.2 mmol scale). 1 H NMR (600 MHz, CDCl3) δ 1.57 (s, 9H), 1.80 (s, 3H), 2.04 (s, 3H), 3.49 (d, J = 15.6 Hz, 2H), 3.90 (m, 4H), 4.18 (m, 2H), 7.22-7.27 (m, 2H), 7.35-7.37 (m, 2H), 7.99 (d, J = 9.0 Hz, 1H), 8.04 (d, J = 10.2 Hz, 1H), 8.16-8.19 (m, 2H), 8.30 (d, J= 9.0 Hz, 1H), 8.45 (s, 1H), 8.85 (d, J= 10.2 Hz, 1H). 13 C NMR (150 MHz, CDCl3) δ 28.0, 30.2, 31.8, 35.1, 48.4, 49.3, 64.2, 110.3, 122.2, 122.5, 122.6, 123.6, 124.9, 125.0, 125.1, 126.5, 126.6, 126.81, 126.85, 126.88, 128.8, 130.3, 130.7, 135.1, 142.2, 142.7, 148.8. HRMS (ESI) m / z calcd for C 34 H 35O2 [M+H] + : 475.2632, found 475.2632.

[0286] Examples 1-13 The compound obtained in Synthesis Example 1-2 was used as the substrate, and the alkyl sulfone compound obtained in Synthesis Example 2-9 was used as the reactant. The reaction was carried out for 30 hours, and the product was purified by PTLC (hexane:ethyl acetate=30:1).

[0287] (1) 2-tert-butyl-6-(2'-butyl)-8-(2'-methyl-1',3'-dioxolan-2-yl)pyrene

[0288] [ka] The target product was obtained as a pale yellow amorphous solid (38.5 mg, 46% isolated yield, 0.2 mmol scale). 1 H NMR (600 MHz, CDCl3) δ 0.97 (t, J = 7.2 Hz, 3H), 1.50 (d, J= 7.2 Hz, 3H), 1.57 (s, 9H), 1.88 (dt, J = 7.2 Hz, 1H), 1.96 (dt, J= 7.2 Hz, 1H), 2.03 (s, 3H), 3.79-3.84 (m, 3H), 4.14-4.19 (m, 2H), 8.03 (d, J = 9.0 Hz, 1H), 8.05 (d, J = 9.6 Hz, 1H), 8.170 (d, J = 7.8 Hz, 1H), 8.173 (d, J = 7.8 Hz, 1H), 8.22 (s, 1H), 8.32 (d, J = 9.0 Hz, 1H), 8.83 (d, J = 9.6 Hz, 1H). 13C NMR (150 MHz, CDCl3) δ 12.4, 21.9, 27.9, 31.1, 31.9, 35.1, 35.8, 64.2, 110.2, 120.9, 121.9, 122.2, 122.6, 123.5, 125.2, 125.9, 126.0, 126.5, 127.4, 128.5, 130.7, 130.8, 135.6, 140.8, 148.8. HRMS (ESI) m / z calcd for C 28 H 33 O2[M+H] + : 401.2475, found 401.2475.

[0289] Examples 1-14 The compound obtained in Synthesis Example 1-2 was used as the substrate, and the alkyl sulfone compounds obtained in Synthesis Examples 2-10 and 2-12 were used as the reactants. The reaction was carried out for 30 hours, and the product was purified by PTLC (hexane: ethyl acetate = 10:1).

[0290] (1) 2-tert-butyl-6-(1'-(ethoxycarbonylethyl))-8-(2'-methyl-1',3'-dioxolan-2-yl)pyrene

[0291] [ka] The target product was obtained as a colorless viscous oil (42.9 mg, 46% isolated yield, 0.2 mmol scale). 1H NMR (600 MHz, CDCl3) δ 1.16 (t, J = 6.9 Hz, 3H), 1.57 (s, 9H), 1.78 (d, J = 7.8 Hz, 3H), 2.01 (s, 3H), 3.82-3.84 (m, 2H), 4.15-4.17 (m, 4H), 4.78 (q, J = 7.8 Hz, 1H), 8.07 (d, J = 9.0 Hz, 1H), 8.10 (d, J = 9.6 Hz, 1H), 8.20 (s, 1H), 8.21 (s, 1H), 8.26 (s, 1H), 8.28 (d, J = 9.6 Hz, 1H), 8.84 (d, J = 9.6 Hz, 1H). 13 C NMR (150 MHz, CDCl3) δ 14.1, 18.7, 27.9, 31.8, 35.1, 41.9, 60.8, 64.2, 110.0, 122.3, 122.4, 122.5, 122.6, 123.3, 125.2, 126.1, 127.0, 127.1, 128.1, 128.5, 130.59, 130.63, 133.9, 135.9, 149.0, 174.9. HRMS (ESI) m / z calcd for C 29 H 33 O4 [M+H] + : 445.2373, found 445.2374.

[0292] Examples 1-15 The compound obtained in Synthesis Example 1-2 was used as the substrate, and the alkyl sulfone compound obtained in Synthesis Example 2-29 was used as the reactant. The reaction was carried out for 30 hours, and the product was purified by PTLC (hexane:ethyl acetate=10:1).

[0293] (1) 2-tert-butyl-6-(1'-(N',N'-dimethylaminocarbonylpropyl))-8-(2'-methyl-1',3'-dioxolan-2-yl)pyrene

[0294] [ka] The desired product was obtained as a white solid (16.1 mg, 35% isolated yield, 0.1 mmol scale). 1 H NMR (600 MHz, CDCl3) δ 1.00 (t, J = 7.5 Hz, 3H), 1.57 (s, 9H), 1.98 (quin, J = 7.5 Hz, 1H), 1.99 (s, 3H), 2.40 (quin, J = 7.5 Hz, 1H), 2.66 (s, 3H), 2.98 (s, 3H), 3.77-3.80 (m, 2H), 4.13-4.17 (m, 2H), 4.57 (t, J = 7.5 Hz, 1H), 8.07 (d, J = 9.0 Hz, 1H), 8.11 (d, J= 9.0 Hz, 1H), 8.21-8.22 (m, 3H), 8.32 (d, J= 9.0 Hz, 1H), 8.83 (d, J = 9.0 Hz, 1H). 13 C NMR (150 MHz, CDCl3) δ 13.0, 27.9, 28.2, 31.8, 35.1, 36.0, 37.1, 47.4, 64.2, 64.3, 109.9, 121.9, 122.4, 122.7, 122.9, 123.3, 125.3, 126.1, 126.9, 127.0, 128.26, 128.33, 130.6, 133.6, 136.2, 149.1, 173.4. HRMS (ESI) m / z calcd for C 30 H 35 O3NNa [M+Na] + : 480.2509, found 480.2509.

[0295] Examples 1-16 The compound obtained in Synthesis Example 1-2 was used as the substrate, and the alkyl sulfone compound obtained in Synthesis Example 2-30 was used as the reactant. The reaction was carried out for 90 hours, and the product was purified by PTLC (hexane:ethyl acetate=1:2).

[0296] (1) 2-tert-butyl-6-(1'-diethoxyphosphorylpropyl)-8-(2'-methyl-1',3'-dioxolan-2-yl)pyrene

[0297] [ka] The target product was obtained as a pale yellow solid (16.2 mg, 31% isolated yield, 0.1 mmol scale). 1 H NMR (400 MHz, CDCl3) δ 0.85 (t, J = 7.2 Hz, 3H), 0.90 (t, J= 7.2 Hz, 3H), 1.23 (t, J = 7.8 Hz, 3H), 1.58 (s, 9H), 2.03 (s, 3H), 2.31-2.38 (m, 1H), 2.45-2.54 (m, 1H), 3,47-3.55 (m, 1H), 3.70-3.78 (m, 2H), 3.97-4.08 (m, 3H), 4.13-4.22 (m, 3H), 8.09 (d, J = 9.6 Hz, 2H), 8.21 (d, J= 9.6 Hz, 1H), 8.28 (d, J = 9.6 Hz, 1H), 8.50 (s, 1H), 8.85 (d, J = 9.6 Hz, 1H). 13 C NMR (150 MHz, CDCl3) δ 12.5 (d, J= 18.8 Hz), 16.2 (d, J = 5.7 Hz), 16.4 (d, J = 5.7 Hz), 23.9, 27.8, 31.8, 35.1, 40.4 (d, J = 136.5 Hz), 61.8 (d, J = 19.2 Hz), 62.3 (d, J = 19.2 Hz), 64.2 (d, J = 4.2 Hz), 109.9, 122.3, 122.4, 122.6, 123.2, 123.61, 123.64, 125.2, 126.0, 126.9, 127.1, 128.0, 129.1 (d, J= 7.1 Hz), 130.2 (d, J = 7.1 Hz), 130.6, 135.5, 149.1. 31P NMR (160 MHz, CDCl3) δ 29.6. HRMS (ESI) m / z calcd for C 31 H 39 O5NaP [M+Na] + : 545.2427, found 545.2429.

[0298] Examples 1-17 The compound obtained in Synthesis Example 1-2 was used as the substrate, and the alkyl sulfone compound obtained in Synthesis Example 2-7 was used as the reactant. The reaction was carried out for 30 hours, and the product was purified by PTLC (hexane:ethyl acetate=40:1).

[0299] (1) 2-tert-butyl-6-(ethoxycarbonylmethyl)-8-(2'-methyl-1',3'-dioxolan-2-yl)pyrene

[0300] [ka] The desired product was obtained as a yellow solid (27.7 mg, 32% isolated yield, 0.2 mmol scale). 1 H NMR (600 MHz, CDCl3) δ 1.22 (t, J = 7.2 Hz, 3H), 1.57 (s, 9H), 2.01 (s, 3H), 3.85-3.87 (m, 2H), 4.15-4.18 (m, 2H), 4.33 (s, 2H), 8.07 (d, J = 9.6 Hz, 1H), 8.09 (d, J = 9.0 Hz, 1H), 8.19-8.22 (m, 4H), 8.84 (d, J = 9.6 Hz, 1H). 13C NMR (150 MHz, CDCl3) δ 14.2, 28.0, 31.9, 35.1, 39.8, 61.0, 64.3, 109.9, 122.56, 122.63, 123.0, 123.1, 125.2, 126.0, 126.2, 127.2, 127.38, 127.43, 128.2, 129.5, 130.5, 130.7, 135.7, 149.1, 171.6. HRMS (ESI) m / z calcd for C 28 H 31 O4 [M+H] + : 431.2217, found 431.2217.

[0301] Examples 1-18 The compound obtained in Synthesis Example 1-2 was used as the substrate, and the alkyl sulfone compound obtained in Synthesis Example 2-11 was used as the reactant. The reaction was carried out for 24 hours, and the product was purified by PTLC (hexane:ethyl acetate=1:2).

[0302] (1) 2-tert-butyl-6-(N',N'-dimethylaminocarbonylmethyl)-8-(2'-methyl-1',3'-dioxolan-2-yl)pyrene

[0303] [ka] The desired product was obtained as a white solid (13.1 mg, 30% isolated yield, 0.1 mmol scale). 1 H NMR (400 MHz, CDCl3) δ 1.57 (s, 9H), 2.00 (s, 3H), 3.04 (s, 3H), 3.09 (s, 3H), 3.82-3.85 (m, 2H), 4.14-4.17 (m, 2H), 4.41 (s, 2H), 8.06 (d, J = 9.6 Hz, 1H), 8.11 (d, J = 10.0 Hz, 1H), 8.12-8.21 (m, 4H), 8.83 (d, J = 9.6 Hz, 1H). 13C NMR (150 MHz, CDCl3) δ 28.0, 31.8, 35.1, 35.9, 37.8, 39.4, 64.2, 109.9, 122.5, 122.6, 123.0, 123.1, 125.1, 125.2, 126.0, 127.1, 127.2, 128.1, 128.2, 129.6, 130.5, 130.8, 135.6, 149.0, 171.1. HRMS (ESI) m / z calcd for C 28 H 31 O3NNa [M+Na] + : 452.2196, found 452.2195.

[0304] Examples 1-19 The compound obtained in Synthesis Example 1-3 was used as the substrate, and 5 equivalents of the alkyl sulfone compound obtained in Synthesis Example 2-19 was used as the reactant, without using zinc acetate, for 90 hours, and the reaction was purified by GPC.

[0305] (1) 2-tert-butyl-6-chloro-8-(1',1'-dimethylpropyl)pyrene

[0306] [ka] The target product was obtained as a yellow solid (28.0 mg, 37% isolated yield, 0.2 mmol scale). 1 H NMR (600 MHz, CDCl3) δ 0.65 (t, J = 7.8 Hz, 3H), 1.57 (s, 9H), 1.71 (s, 6H), 2.24 (q, J = 7.8 Hz, 2H), 8.03 (d, J = 9.6 Hz, 1H), 8.06 (s, 1H), 8.08 (d, J = 9.0 Hz, 1H), 8.20 (s, 2H), 8.40 (d, J = 9.0 Hz, 1H), 8.63 (d, J = 9.6 Hz, 1H). 13C NMR (150 MHz, CDCl3) δ 9.7, 30.4, 31.8, 35.1, 35.6, 40.3, 122.5, 122.7, 123.0, 123.1, 125.4, 126.1, 126.2, 126.6, 127.0, 127.9, 128.2, 128.7, 130.3, 131.2, 143.4, 149.4. HRMS (DART) m / z calcd for C 25 H 28 Cl [M+H] + : 363.1880, found 363.1881.

[0307] Examples 1-20 The compound obtained in Synthesis Example 1-4 was used as the substrate, and the alkyl sulfone compound obtained in Synthesis Example 2-19 was used as the reactant, and the reaction was carried out for 30 hours, followed by purification by GPC.

[0308] (1) 2-tert-butyl-6-(1',1'-dimethylpropyl)-8-(trimethylsilyl)pyrene

[0309] [ka] The desired product was obtained as a yellow solid (36.9 mg, 46% isolated yield, 0.2 mmol scale). 1 H NMR (600 MHz, CDCl3) δ 0.59 (s, 9H), 0.69 (t, J = 7.8 Hz, 3H), 1.57 (s, 9H), 1.73 (s, 6H), 2.25 (q, J= 7.8 Hz, 2H), 8.02 (d, J = 9.0 Hz, 1H), 8.03 (d, J = 9.0 Hz, 1H), 8.17-8.18 (m, 2H), 8.21 (s, 1H), 8.28 (d, J = 9.0 Hz, 1H), 8.66 (d, J = 9.0 Hz, 1H). 13C NMR (150 MHz, CDCl3) δ 0.7, 9.8, 30.4, 31.9, 35.1, 35.8, 40.3, 121.9, 122.3, 123.8, 125.76, 125.81, 126.4, 126.5, 127.6, 129.7, 130.2, 130.8, 131.2, 134.2, 134.3, 140.9, 148.6. HRMS (DART) m / z calcd for C 28 H 37 Si [M+H] + : 401.2664, found 401.2660.

[0310] Examples 1-21 The compound obtained in Synthesis Example 1-5 was used as the substrate, and the alkyl sulfone compound obtained in Synthesis Example 2-19 was used as the reactant, and the reaction was carried out for 90 hours, followed by purification by GPC.

[0311] (1) 1,6-dimethyl-8-(1',1'-dimethylpropyl)-3-(2'-methyl-1',3'-dioxolan-2-yl)pyrene

[0312] [ka] The desired product was obtained as a yellow solid (30.1 mg, 39% isolated yield, 0.2 mmol scale). 1 H NMR (600 MHz, CDCl3) δ 0.64 (t, J = 7.8 Hz, 3H), 1.72 (s, 6H), 2.01 (s, 3H), 2.26 (q, J = 7.8 Hz, 2H), 2.965 (s, 3H), 2.971 (s, 3H), 3.83-3.85 (m, 2H), 4.14-4.16 (m, 2H), 7.89 (s, 1H), 8.139 (d, J = 9.6 Hz, 1H), 8.141 (s, 1H), 8.18 (d, J = 9.6 Hz, 1H), 8.72 (d, J = 9.6 Hz, 1H), 8.85 (d, J = 9.6 Hz, 1H).13 C NMR (150 MHz, CDCl3) δ 9.7, 20.1, 20.5, 28.0, 30.7, 35.8, 40.0, 64.2, 110.1, 120.9, 122.4, 124.3, 125.67, 125.69, 126.61, 126.64, 126.7, 127.4, 127.5, 127.8, 128.8, 130.8, 131.2, 135.0, 142.1. HRMS (ESI) m / z calcd for C 27 H 31 O2 [M+H] + : 387.2319, found 387.2319.

[0313] Examples 1-22 The compound obtained in Synthesis Example 1-6 was used as the substrate, and the alkyl sulfone compound obtained in Synthesis Example 2-19 was used as the reactant. The reaction was carried out for 90 hours, and the mixture was purified by PTLC (hexane:ethyl acetate=5:1).

[0314] (1) 1-(1',1'-dimethylpropyl)-3,6,8-tris(2'-methyl-1',3'-dioxolan-2-yl)pyrene

[0315] [ka] The target product was obtained as a pale yellow solid (37.8 mg, 71% isolated yield, 0.1 mmol scale). 1H NMR (600 MHz, CDCl3) δ 0.66 (t, J = 7.8 Hz, 3H), 1.75 (s, 6H), 2.026 (s, 6H), 2.034 (s, 3H), 2,26 (q, J = 7.8 Hz, 2H), 3.82-3.85 (m, 2H), 4.17-4.19 (m, 2H), 8.40 (s, 1H), 8.59 (s, 1H), 8.73 (d, J = 10.2 Hz, 1H), 8.85 (d, J = 10.2 Hz, 1H), 8.87 (d, J = 10.2 Hz, 1H), 8.91 (d, J = 10.2 Hz, 1H). 13 C NMR (150 MHz, CDCl3) δ 9.7, 28.0, 30.8, 35.8, 40.3, 64.18, 64.26, 64.29, 110.2, 110.3, 121.7, 123.5, 123.7, 124.1, 125.0, 125.4, 126.1, 127.4, 127.6, 128.0, 128.8, 135.1, 135.2, 142.2. HRMS (ESI) m / z calcd for C 33 H 39 O6 [M+H] + : 531.2741, found 531.2744.

[0316] Examples 1-23 The compound obtained in Synthesis Example 1-2 was used as the substrate, and the alkyl sulfone compound obtained in Synthesis Example 2-34 was used as the reactant. The reaction was carried out for 90 hours, and the product was purified by column chromatography (hexane:ethyl acetate=8:1 to 3:1).

[0317] (1) 3-(7-tert-butyl-3-(2'-methyl-1',3'-dioxolan-2-yl))-3,3-dimethylpropyl 1'-tert-butyl-N'-(tert-butoxycarbonyl)-L-glutamate

[0318] [ka] The target product was obtained as a white amorphous solid (50.1 mg, 70% isolated yield, 0.1 mmol scale). 1 H NMR (600 MHz, CDCl3) δ 1.39 (s, 9H), 1.40 (s, 9H), 1.57 (s, 9H), 1.62-1.70 (m, 1H), 1.90-1.97 (m, 1H), 2.02 (s, 1H), 2.04-2.08 (m, 1H), 2.11-2.18 (m, 1H), 2.59-2.63 (m, 1H), 3.83-3.88 (m, 4H), 4.04-4.08 (m, 1H), 4.16-4.18 (m, 2H), 4.94 (d, J = 8.4 Hz, 1H), 8.04 (d, J = 9.6 Hz, 1H), 8.06 (d, J = 9.6 Hz, 1H), 8.18 (s, 1H), 8.19 (s, 1H), 8.34 (s, 1H), 8.63 (d, J = 9.6 Hz, 1H), 8.83 (d, J = 9.6 Hz, 1H). 13 C NMR (150 MHz, CDCl3) δ 27.8, 27.9, 28.0, 28.2, 30.1, 31.20, 31.23, 31.8, 35.0, 38.6, 41.0, 53.2, 62.4, 64.2, 79.6, 82.0, 110.2, 122.2, 122.46, 122.54, 123.5, 125.0, 125.1, 126.6, 126.8, 127.0, 128.9, 130.1, 130.7, 135.0, 140.1, 148.9, 155.3, 171.2, 172.6. HRMS (ESI) m / z calcd for C 43 H 57 O8NNa [M+Na] + : 738.3976, found 738.3972.

[0319] Examples 1-23 The compound obtained in Synthesis Example 1-2 was used as the substrate, and the alkyl sulfone compound obtained in Synthesis Example 2-16 was used as the reactant, and the reaction was carried out for 90 hours.

[0320] (1) 3-(1'-(7'-tert-butyl-3'-acetylpyrenyl))-5α-androstan-17-one

[0321] [ka] Prior to purification, the acetal was deprotected as follows: The crude product (0.1 mmol), p-toluenesulfonic acid monohydrate (28.2 mg, 0.15 mmol), and acetone (1.5 mL) were added to a 10 mL sealable glass vessel equipped with a magnetic stir bar. The mixture was stirred at 70 °C for 3 h. After cooling to room temperature, K2CO3 (100 mg) was added to the mixture, which was stirred at room temperature for 1 h, filtered, and concentrated under reduced pressure. The residue was purified by PTLC (hexane:ethyl acetate = 1:8) (35%, dr = 1.5:1). Major: 1 H NMR (600 MHz, CDCl3) δ 0.79-0.83 (m, 1H), 0.87-0.89 (m, 4H), 0.96-1.01 (m, 4H), 1.21-1.65 (m, 18H), 1.68-1.75 (m, 2H), 1.80-1.88 (m, 3H), 1.90-2.00 (m, 4H), 2.10 (dt, J = 9.6, 19.2 Hz, 1H), 2.46 (dd, J = 9.6, 20.4 Hz, 1H), 2.92 (s, 3H), 3.69-3.73 (m, 1H), 8.13 (d, J = 9.6 Hz, 1H), 8.19 (d, J = 9.6 Hz, 1H), 8.25-8.27 (m, 3H), 8.34 (d, J = 9.6 Hz, 1H). 13C NMR (150 MHz, CDCl3) δ 12.3, 13.8, 20.3, 21.7, 28.5, 29.9, 30.8, 30.9, 31.5, 31.8, 35.1, 35.2, 35.9, 36.1, 36.3, 39.2, 40.0, 47.5, 47.8, 51.4, 54.7, 122.3, 123.0, 123.2, 123.3, 123.6, 124.6, 125.4, 127.3, 129.0, 129.5, 130.6, 130.7, 130.8, 132.3, 139.9, 149.4, 203.0, 221.4. HRMS (ESI) m / z calcd for C 41 H 49 O2[M+H] + : 573.3727, found 573.3728。 Minor: 1 H NMR (600 MHz, CDCl3) δ 0.74-0.79 (m, 1H), 0.83-0.88 (m, 5H), 1.02 (s, 3H), 1.13-1.15 (m, 1H), 1.21-1.63 (m, 17H), 1.69-1.74 (m, 2H), 1.82-1.91 (m, 4H), 2.05 (dt, J = 9.0, 19.4 Hz, 1H), 2.18 (dt, J = 6.8, 13.4 Hz, 1H), 2.29-2.37 (m, 2H), 2.42 (dd, J = 6.8, 19.4 Hz, 1H), 2.93 (s, 3H), 4.18 (t, J = 6.3 Hz, 1H), 8.14 (d, J = 9.6 Hz, 1H), 8.18 (d, J = 9.0 Hz, 1H), 8.257 (d, J = 9.6 Hz, 1H), 8.258 (s, 2H), 8.53 (s, 1H), 8.97 (d, J = 9.0 Hz, 1H). 13C NMR (150 MHz, CDCl3) δ 12.0, 13.8, 20.1, 21.7, 25.7, 28.6, 30.6, 30.7, 31.5, 31.8, 33.0, 34.3, 35.0, 35.2, 35.8, 36.0, 36.1, 41.3, 47.8, 51.3, 55.0, 122.9, 123.2, 123.4, 124.6, 125.5, 125.6, 127.5, 129.1, 129.4, 130.4, 130.6, 130.9, 131.2, 139.7, 149.4, 202.8, 221.5. HRMS (ESI) m / z calcd for C 41 H 49 O2[M+H] + : 573.3727, found 573.3727.

[0322] Examples 1-24 Using fluoranthene as the substrate and the alkyl sulfone compound obtained in Synthesis Example 2-19 as the reactant, the reaction was carried out for 24 hours, and the product was purified by GPC.

[0323] (1) 3-(1',1'-dimethylpropyl)fluoranthene

[0324] [ka] The desired product was obtained as a yellow solid (23.3 mg, 43% isolated yield, 0.2 mmol scale). 1 H NMR (600 MHz, CDCl3) δ 0.66 (t, J = 7.5 Hz, 3H), 1.60 (s, 6H), 2.12 (q, J = 7.5 Hz, 2H), 7.33-7.34 (m 2H), 7.52 (d, J = 7.2 Hz, 1H), 7.57 (dd, J = 6.6, 8.4 Hz, 1H), 7.82 (d, J = 6.6 Hz, 1H), 7.84-7.87 (m, 2H), 7.89 (d, J = 6.6 Hz, 1H), 8.33 (d, J = 8.4 Hz, 1H).13 C NMR (150 MHz, CDCl3) δ 9.5, 30.4, 36.6, 40.2, 119.1, 119.8, 121.0, 121.1, 126.1, 126.5, 126.6, 127.2, 127.4, 129.1, 133.6, 135.5, 137.9, 138.9, 139.5, 146.3. HRMS (DART) m / z calcd for C 21 H 21 [M+H] + : 273.1643, found 273.1637.

[0325] Examples 1-25 Using perylene as the substrate, the alkyl sulfone compound obtained in Synthesis Example 2-19 as the reactant, and dimethylacetamide (DMA) as the solvent, the reaction was carried out for 90 hours under irradiation with visible light at a wavelength of 525 nm from an LED, and then purified by GPC.

[0326] (1) 3-(1',1'-dimethylpropyl)perylene

[0327] [ka] The desired product was obtained as a yellow solid (11.5 mg, 36% isolated yield, 0.1 mmol scale). 1 H NMR (600 MHz, CDCl3) δ 0.68 (t, J = 7.8 Hz, 3H), 1.56 (s, 6H), 2.11 (q, J = 7.8 Hz, 2H), 7.45-7.50 (m, 4H), 7.66 (dd, J = 4.8, 7.8 Hz, 2H), 8.13 (d, J = 7.8 Hz, 1H), 8.17 (dd, J = 7.8, 9.0 Hz, 2H), 8.21 (d, J= 7.8 Hz, 1H), 8.30 (d, J = 9.0 Hz, 1H). 13C NMR (150 MHz, CDCl3) δ 9.6, 30.0, 34.9, 39.8, 119.7, 119.8, 120.00, 120.05, 125.0, 125.7, 126.3, 126.56, 126.59, 127.2, 127.5, 128.3, 129.5, 130.0, 131.4, 131.7, 132.0, 133.1, 134.5, 144.3. HRMS (DART) m / z calcd for C 25 H 25 [M+H] + : 325.1956, found 325.1953.

[0328] Examples 1-26 Using thieno[3,2-b]thiophene as the substrate and the alkylsulfone compound obtained in Synthesis Example 2-19 as the reactant, the reaction was carried out for 42 hours under irradiation with visible light at a wavelength of 427 nm from an LED, and then purified by GPC.

[0329] (1) 2-(1',1'-dimethylpropyl)thieno[3,2-b]thiophene

[0330] [ka] The target product was obtained as a yellow solid (15.0 mg, 36% isolated yield, 0.2 mmol scale). 1 H NMR (600 MHz, CDCl3) δ 0.82 (t, J = 7.5 Hz, 3H), 1.37 (s, 6H), 1.69 (q, J = 7.5 Hz, 2H), 6.97 (s, 1H), 7.18 (d, J = 4.8 Hz, 1H), 7.26 (d, J = 4.8 Hz, 1H). 13 C NMR (150 MHz, CDCl3) δ 9.2, 29.5, 37.9, 38.7, 114.5, 119.5, 125.3, 137.1, 138.4, 158.8. HRMS (ESI) m / z calcd for C 11 H14 S2 [M+H] + : 211.0610, found 211.0611.

[0331] (2) 2,5-bis(1',1'-dimethylpropyl)thieno[3,2-b]thiophene

[0332] [ka] The desired product was obtained as an orange solid (6.7 mg, 12% isolated yield, 0.2 mmol scale). 1 H NMR (400 MHz, CDCl3) δ 0.82 (t, J = 7.2 Hz, 6H), 1.35 (s, 12H), 1.67 (q, J = 7.2 Hz, 4H), 6.89 (s, 2H). 13 C NMR (150 MHz, CDCl3) δ 9.2, 29.6, 37.9, 38.5, 114.7, 136.2, 156.8. HRMS (ESI) m / zcalcd for C 16 H 25 S2 [M+H] + : 281.1392, found 281.1392.

[0333] Examples 1-27 The compound obtained in Synthesis Example 1-7 was used as the substrate, and the alkyl sulfone compound obtained in Synthesis Example 2-19 was used as the reactant. The reaction was carried out for 90 hours without using zinc acetate, and the product was purified by PTLC (hexane:ethyl acetate=20:1).

[0334] (1) N-(tert-butoxycarbonyloxy)-3-(1',1'-dimethylpropyl)benzo[f]indole

[0335] [ka] The desired product was obtained as a yellow amorphous solid (16.4 mg, 51% isolated yield, 0.1 mmol scale). 1 H NMR (600 MHz, CDCl3) δ 0.71 (t, J = 7.2 Hz, 3H), 1.55 (s, 9H), 1.84 (s, 6H), 2.27 (q, J = 7.2 Hz, 2H), 7.31 (d, J = 4.8 Hz, 1H), 7.38-7.40 (m, 2H), 7.81 (d, J = 4.8 Hz, 1H), 7.96-7.97 (m, 1H), 8.57-8.59 (m, 1H), 9.11 (s, 1H). 13 C NMR (150 MHz, CDCl3) δ 9.9, 28.6, 32.9, 36.6, 41.3, 43.0, 110.3, 114.9, 123.0, 123.7, 127.0, 127.1, 129.0, 129.4, 130.4, 133.5, 136.5, 136.7, 176.4. HRMS (ESI) m / zcalcd for C 22 H 28 ON [M+H] + : 322.2165, found 322.2165.

[0336] The above results are summarized in Table 1.

[0337] [Table 1]

[0338] Comparative Example 1 When the substrates shown below were used, no reaction occurred or only a trace of reaction occurred.

[0339] [ka]

[0340] Example 2: Reaction conditions (common operation) A 10 mL sealable glass vessel containing a magnetic stir bar was flame dried under vacuum, cooled to room temperature, and then backfilled with argon. 2-tert-butylpyrene (12.9 mg, 0.05 mmol), reactant (0.15 mmol), base (0.15 mmol), and additive (0.15 mmol) were added to the glass vessel. The mixture was evaporated under vacuum and backfilled with argon. This cycle was repeated two more times. Under an argon atmosphere, solvent (0.25 mL) was added, the reaction vessel was sealed, and the mixture was stirred while irradiating visible light at a wavelength of 456 nm using an LED. After the reaction was complete, the mixture was diluted with ethyl acetate (approximately 2 mL) and biphenyl (10 mg) as an internal standard. An aliquot was passed through a pad of silica gel, and the filtrate was analyzed by HPLC.

[0341] Example 2-1: Comparison of bases The compound obtained in Synthesis Example 2-19 was used as a reactant, no additive was used, dimethyl sulfoxide (DMSO) was used as a solvent, and various bases were used. The conversion rates and yields were evaluated in Table 2.

[0342] [Table 2]

[0343] Example 2-2: Comparison of solvents The conversion and yield when the compound obtained in Synthesis Example 2-19 was used as a reactant, Na2CO3 was used as a base, no additives were used, and various solvents were used were evaluated in Table 3. In Table 3, DMSO represents dimethyl sulfoxide, and DMF represents dimethylformamide.

[0344] [Table 3]

[0345] Example 2-3: Comparison of additives The conversion and yield when the compound obtained in Synthesis Example 2-19 was used as a reactant, Na2CO3 was used as a base, dimethyl sulfoxide (DMSO) was used as a solvent, and various additives were used were evaluated in Table 4. In Table 4, NaOAc represents sodium acetate, KOAc represents potassium acetate, Mg(OTf)2 represents magnesium trifluoromethanesulfonate, Zn(OTf)2 represents zinc trifluoromethanesulfonate, Zn(OAc)2 represents zinc acetate, and Bu4NOTf represents tetrabutylammonium trifluoromethanesulfonate.

[0346] [Table 4]

[0347] Example 2-4: Comparison of additive amounts The compound obtained in Synthesis Example 2-19 was used as the reactant, Na2CO3 was used as the base, dimethyl sulfoxide (DMSO) was used as the solvent, and the amount of zinc acetate used as the additive was varied. The conversion rate and yield were evaluated in Table 5. In Table 5, Zn(OAc)2 represents zinc acetate.

[0348] [Table 5]

[0349] Example 2-5: Comparison of reactants The conversion and yield for various reactants using Na2CO3 as the base, dimethyl sulfoxide (DMSO) as the solvent, and no additives were evaluated below.

[0350] [ka]

[0351] Example 2-6: Wavelength Comparison The yields were evaluated in Table 6 when the compound obtained in Synthesis Example 2-19 was used as a reactant, Na2CO3 was used as a base, dimethyl sulfoxide (DMSO) was used as a solvent, no additives were used, and the wavelength of visible light was changed.

[0352] [Table 6]

[0353] [Example 3: Multiple Operation]

[0354] [ka] A 10 mL sealable glass vessel containing a magnetic stir bar was flame-dried under vacuum, cooled to room temperature, and then backfilled with argon. Pyrene (10.1 mg, 0.05 mmol), the alkyl sulfone compound (110.5 mg, 0.25 mmol) obtained in Synthesis Example 2-24, zinc acetate (Zn(OAc)2; 27.5 mg, 0.15 mmol), and Na2CO3 (26.5 mg, 0.25 mmol) were added to the vessel. The mixture was evaporated under vacuum and refilled with argon. This cycle was repeated two more times. Dimethyl sulfoxide (DMSO; 0.25 mL) was added under an argon atmosphere, the reaction vessel was sealed, and the mixture was stirred at approximately 30–35 °C for 90 h under visible light irradiation at 456 nm using an LED. The mixture was passed through a pad of silica gel and washed successively with ethyl acetate:hexane = 1:20 (approximately 200 mL). The filtrate was concentrated under reduced pressure. The reaction was repeated two more times using the crude mixture (reaction times were 40 and 90 hours, respectively). The residue was purified by GPC and PTLC (hexane:ethyl acetate=30:1) to give 1,3,6,8-tetrakis(3'-tert-butyldimethylsilyl)oxy-1',1'-dimethylpropyl)pyrene (17.2 mg, 34%) as a pale yellow solid. 1H NMR (600 MHz, CDCl3) δ -0.14 (s, 24H), 0.78 (s, 36H), 1.77 (s, 24H), 2.51 (t, J = 7.2 Hz, 8H), 3.42 (t, J= 7.2 Hz, 8H), 8.08 (s, 2H), 8.62 (s, 2H). 13 C NMR (150 MHz, CDCl3) δ-5.4, 18.1, 25.9, 31.5, 39.1, 45.7, 60.8, 123.4, 124.0, 127.1, 128.6, 140.3. HRMS (ESI) m / z calcd for C 60 H 106 O4NaSi4[M+Na] + : 1025.7060, found 1025.7062.

[0355] [Synthesis Example 3: Rearrangement of Substituent Position]

[0356] [ka] A 10 mL sealable glass vessel containing a magnetic stir bar was flame dried under vacuum, cooled to room temperature, and then backfilled with argon. 1,7-di-tert-butylpyrene (15.9 mg, 0.05 mmol) and CHCl (0.5 mL) were added to the vessel. Trifluoromethanesulfonic acid (4.4 μL, 0.05 mmol) was added to the mixture, which was then stirred at 40 °C for 1 h. KCO (10 mg) was added to the mixture, which was then stirred at room temperature for 1 h. 1,3-Dimethoxybenzene (10 mg) and ethyl acetate (2 mL) were added as an internal standard to the mixture, which was then passed through a silica gel pad. The filtrate was analyzed by GC, and the yields of 2,7-di-tert-butylpyrene and 2-tert-butylpyrene were 44% and 47%, respectively.

[0357] Comparative Example 2: Reaction under reducing conditions

[0358] [ka] We have reported that alkyl radicals are generated from alkyl sulfone compounds using zinc and 1,10-phenanthroline as reducing agents. However, when we attempted the reaction without light irradiation, the alkyl sulfone compound was completely consumed, and although it was clear that alkyl radicals were generated, the target product was not detected. This indicates that the alkyl radicals generated from alkyl sulfone compounds do not react directly with polycyclic aromatic compounds, suggesting the need for visible light irradiation.

[0359] Comparative Example 3: Reaction with alkylsulfinate

[0360] [ka] Since it has been reported that alkyl radicals are generated from alkylsulfinates by oxidative deactivation with a photoredox catalyst, we attempted to alkylate pyrene under standard conditions using sodium alkylsulfinate instead of alkylsulfone compounds. However, the target product was not detected, suggesting that the same reaction as in the present invention does not proceed when alkylsulfinate salts are used.

[0361] The sodium alkylsulfinate was synthesized as follows: 5-((1',1'-dimethyl-3'-phenylpropyl)sulfonyl)-1-phenyl-1H-tetrazole (356 mg, 1 mmol) and dry methanol (2.5 mL) were added to a 50 mL flask, and the mixture was stirred at room temperature for 30 minutes. Water was added to the mixture, and the mixture was washed with ethyl acetate (three times). The aqueous phase was evaporated under reduced pressure to obtain sodium alkylsulfinate (223 mg, 95%) as a white solid. 1 H NMR (400 MHz, CD3OD) δ 1.05 (s, 6H), 1.70-1.74 (m, 2H), 2.63-2.68 (m, 2H), 7.10-7.13 (m, 1H), 7.18-7.25 (m, 4H). HRMS (ESI) m / z calcd for C11 H 15 O2S [M-Na] - : 211.0787, found 211.0788.

[0362] [Example 4: Visible light on / off test] A 10 mL sealable glass vessel containing a magnetic stir bar was flame-dried under vacuum, cooled to room temperature, and then backfilled with argon. 2-tert-butylpyrene (51.7 mg, 0.20 mmol), the alkyl sulfone compound (0.60 mmol) obtained in Synthesis Example 2-19, Na2CO3 (63.6 mg, 0.60 mmol), and biphenyl (40.0 mg, internal standard) were added to the glass vessel. The mixture was evaporated under vacuum and refilled with argon. This cycle was repeated two more times. Dimethyl sulfoxide (DMSO; 1.0 mL) was added under an argon atmosphere, the reaction mixture was sealed, and the mixture was stirred while irradiating with visible light at a wavelength of 456 nm using an LED. During the period (OF), the light was turned off, and the vessel was wrapped in aluminum foil to protect it from light. During the period (O), the aluminum foil was removed, and the reaction mixture was irradiated with visible light at a wavelength of 456 nm using an LED as described above. After a certain time period, aliquots were taken and the progress of the reaction was monitored by HPLC analysis, the results of which are shown in Figure 1.

[0363] As a result, it can be seen that the reaction proceeds upon irradiation with light, whereas the reaction hardly proceeds in the absence of light irradiation.

Claims

1. General formula (1): 【Chemical 1】 [In the formula, Ar １ represents a fused aromatic ring having 4 to 6 rings (excluding a chrysene ring, a triphenylene ring, and a dibenzo[g,p]chrysene ring), a thienothiophene ring, a benzo[f]indole ring, a benzodithiophene ring, a benzodifuran ring, or a naphthothiophene ring. １ represents an alkyl group, and n represents an integer of 1 to 4. A method for producing a compound represented by the formula: The Ar １ a polycyclic aromatic compound consisting of General formula (2A) or (2B): 【Chemistry 2】 [In the formula, R １ is the same as above. ２ represents an alkyl group or an aryl group. ３ represents a halogen atom, an alkyl group, or an alkoxy group, and m represents an integer of 0 to 4. and a compound represented by A step of reacting under ultraviolet or visible light irradiation A manufacturing method comprising:

2. The R １ The method according to claim 1, wherein is a tertiary alkyl group.

3. The Ar １ The method according to claim 1 or 2, wherein is a pyrene ring, a fluoranthene ring, a perylene ring, a thienothiophene ring, a benzo[f]indole ring, a benzodithiophene ring, a benzodifuran ring, or a naphthothiophene ring.

4. The method according to claim 1 or 2, wherein the reaction is carried out in the presence of a metal compound and / or an ammonium salt.

5. 5. The method according to claim 4, wherein the metal constituting the metal compound is at least one metal selected from the group consisting of alkali metals, alkaline earth metals, and zinc.

6. The method according to claim 1 or 2, wherein the reaction is carried out in the presence of a base.

7. The method according to claim 6, wherein the base is at least one selected from the group consisting of carbonates, phosphates, acetates, hydroxides, alkoxides, and amines.

8. The method according to claim 1 or 2, wherein the reaction is carried out in the presence of an organic solvent.

9. The method according to claim 8, wherein the organic solvent is an amide solvent and / or a sulfoxide solvent.

10. 3. The method according to claim 1, wherein the ultraviolet light or visible light has a peak wavelength of 300 to 800 nm.

11. General formulas (1A1) to (1A5): 【Chemistry 3】 [In the formula, R １ａ , R １ｅ , R １ｇ , R １ｋ and R １ｍ are the same or different and represent an alkyl group. １ｂ , R １ｃ , R １ｄ , R １ｆ , R １ｈ , R １ｉ , R １ｊ and R １ｌ are the same or different and represent a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, an aryl group, a heterocyclic group, an amino group, an alkylcarbonyl group, an alkoxycarbonyl group, an aminocarbonyl group, a silyl group, or a boronic acid or ester group thereof. ２ａ , R ２ｂ , R ２ｃ , R ２ｄ , R ２ｅ and R ２ｆ are the same or different and represent a halogen atom, an alkyl group, an alkoxy group, an aryl group, a heterocyclic group, an amino group, an alkylcarbonyl group, an alkoxycarbonyl group, an aminocarbonyl group, a silyl group, or a boronic acid or ester group thereof. m1 is an integer of 0 to 6. m2 and m3 are the same or different and represent an integer of 0 to 8. m4 is an integer of 0 to 2. m5 is an integer of 0 to 7.] A compound represented by any of the following:

12. General formula (2A1): 【Chemistry 4】 [In the formula, R １ represents an alkyl group. ２ａ represents an alkyl group substituted with an aryl group or an aryl group substituted with an alkyl group.] A compound represented by the formula:

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