JP2012240933A - Method for producing phenylboronic acid ester - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for producing phenylboronic acid esters in good yield from diborons and aryl halides by using a nickel catalyst and a base.SOLUTION: In the method for producing phenylboronic acid esters represented by general formula (3), wherein A is an ethylene group or the like which may be substituted by a methyl group, Ris a fluorine atom or the like, and m is an integer of 0-5; diborons and a chlorobenzene derivative are reacted with each other by using a trimethylphosphine coordinated nickel catalyst and alkoxides.

Description

  The present invention relates to a method for producing phenylboronic acid esters.

  Phenylboronic acid esters are industrially useful compounds as production intermediates for physiologically active substances such as pharmaceuticals and agricultural chemicals, and electronic materials such as liquid crystals and organic EL devices. As a method for producing phenylboronic acid esters from boron compounds and aryl halides, only two examples of nickel catalysts have been known so far. Patent Document 1 discloses a method in which diboron and aryl halide are reacted in the presence of a triphenylphosphine coordinated nickel catalyst and amines. Non-Patent Documents 1 and 2 include alkoxyborane and aryl halides, triphenylphosphine, tricyclohexylphosphine, 1,1′-bis (diphenylphosphino) ferrocene or diphenylphosphinopropane coordinated nickel catalyst. A method of reacting in the presence of amines is disclosed.

International Publication No. 2010/110782 Pamphlet

The Journal of Organic Chemistry, 75, 5438-5542, 2010. The Journal of Organic Chemistry, 75, 7822-7828, 2010.

  In the method described in Patent Document 1, when aryl halides having a functional group such as an alkyl group or an amino group are used as a substrate, the yield of the target product is only 60% and 40%, respectively. Further, it is described that a target product cannot be obtained when an inorganic base such as potassium acetate is used. Since the methods described in Non-Patent Documents 1 and 2 use alkoxyborane as a raw material, production examples of phenylboronic acid esters having an alkenyl group or an amino group that may react with the material are specified. Absent.

  An object of the present invention is to provide a method for producing phenylboronic acid esters with good yield from diboron and halogenated aryls which may have various functional groups, using a nickel catalyst and a base.

As a result of intensive studies in view of the above problems, the present inventors have found that phenylboronic acid esters that may have various functional groups from diborones and chlorobenzene derivatives in the presence of a trimethylphosphine coordinated nickel catalyst and alkoxides. The present invention has been completed by finding that it can be produced in good yield.

  That is, the present invention relates to the general formula (1)

（式中、Ａは、メチル基で置換されていてもよいエチレン基またはトリメチレン基を表す。）で表されるジボロン類と、一般式（２）

(Wherein A represents an ethylene group or trimethylene group which may be substituted with a methyl group) and a general formula (2)

（式中、Ｒ^１は、フッ素原子；フッ素原子または炭素数１〜４のアルコキシ基で置換されていてもよい炭素数１〜８のアルキル基；（炭素数１〜４のアルコキシ）カルボニル基；塩素原子で置換されていてもよい炭素数１〜４のアルコキシ基；炭素数２〜４のアルケニル基；炭素数２〜９のアシル基で置換されていてもよいアミノ基；炭素数２〜９のアシル基；モルホリノ基；フェニルカルボニル基；シアノ基；カルバモイル基；２，３−ジヒドロ−１Ｈ−ナフト［１，８−デ］−１，３，２−ジアゾボリニル基を表す。隣接するＲ^１同士は、結合する炭素と一体となって、芳香族炭化水素環を形成してもよい。ｍは、０〜５の整数を表す。ｍが２〜５のとき、Ｒ^１は、同一または相異なっていてもよい。）で表されるクロロベンゼン誘導体を反応させて、一般式（３）

(Wherein R ¹ represents a fluorine atom; a fluorine atom or an alkyl group having 1 to 8 carbon atoms which may be substituted with a fluorine atom or an alkoxy group having 1 to 4 carbon atoms; (alkoxy having 1 to 4 carbon atoms) carbonyl group; An alkoxy group having 1 to 4 carbon atoms which may be substituted with a chlorine atom; an alkenyl group having 2 to 4 carbon atoms; an amino group which may be substituted with an acyl group having 2 to 9 carbon atoms; A morpholino group, a phenylcarbonyl group, a cyano group, a carbamoyl group, a 2,3-dihydro-1H-naphtho [1,8-de] -1,3,2-diazoborinyl group, and adjacent R ¹ groups. May form an aromatic hydrocarbon ring together with the carbon to be bonded, m represents an integer of 0 to 5. When m is 2 to 5, R ¹ is the same or different. Chlorobenzene derivative represented by Are reacted, the general formula (3)

（式中、Ａ、Ｒ^１およびｍは、前記と同じ内容を表す。）で表されるフェニルボロン酸エステル類を製造する方法において、トリメチルホスフィン配位ニッケル触媒および一般式（４）

(Wherein A, R ¹ and m represent the same contents as described above), the trimethylphosphine coordinated nickel catalyst and the general formula (4)

（式中、Ｒ^２は、水素原子またはフッ素原子を表す。Ｒ^３およびＲ^４は、各々独立に、水素原子またはメチル基を表す。Ｍは、アルカリ金属原子を表す。ｎは、１〜１１の整数を表す。）で表されるアルコキシド類を用いることを特徴とするフェニルボロン酸エステル類の製造方法に関するものである。

(In the formula, R ² represents a hydrogen atom or a fluorine atom. R ³ and R ⁴ each independently represents a hydrogen atom or a methyl group. M represents an alkali metal atom. N represents 1 to 11). It is related with the manufacturing method of phenyl boronic acid ester characterized by using the alkoxide represented by this.

  The present invention is described in detail below.

  First, the diboron (1), chlorobenzene derivative (2) and phenylboronic acid ester (3) of the present invention will be described.

Specific examples of the ethylene group or trimethylene group represented by A and optionally substituted with a methyl group include ethylene group, 1,2-dimethylethylene group, 1,1,2,2-tetramethylethylene. Examples include a group, trimethylene group, 2,2-dimethyltrimethylene group, 1,1,3-trimethyltrimethylene group and the like. In view of good yield, 1,1,2,2-tetramethylethylene group or 1,1,3-trimethyltrimethylene group is preferable.
As diborones (1), commercially available products can be used, but by a method using tetrakis (dimethylamido) diboron and a corresponding diol described in Organic Synthesis, Vol. 77, p. 176, 2000 or a method analogous thereto. Can be prepared.

The alkyl group having 1 to 8 carbon atoms which may be substituted with a fluorine atom represented by R ¹ or an alkoxy group having 1 to 4 carbon atoms may be either linear or branched, specifically, a methyl group , Ethyl group, propyl group, isopropyl group, butyl group, sec-butyl group, tert-butyl group, pentyl group, isopentyl group, tert-pentyl group, hexyl group, octyl group, trifluoromethyl group, 2,2,2 -Trifluoroethyl group, 1,1,1,3,3,3-hexafluoroisopropyl group, 1-methoxyethyl group, 1-methoxypropyl group, 1-methoxybutyl group, dimethoxymethyl group, diethoxymethyl group, etc. Can be illustrated.

The (C 1-4 alkoxy) carbonyl group represented by R ¹ may be either linear or branched, and specifically includes a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, an isopropoxycarbonyl group, Examples include butoxycarbonyl group, sec-butoxycarbonyl group, and tert-butoxycarbonyl group.

The alkoxy group having 1 to 4 carbon atoms which may be substituted with a chlorine atom represented by R ¹ may be linear or branched, and specifically includes a methoxy group, an ethoxy group, a propoxy group, isopropyloxy Group, butoxy group, sec-butyloxy group, tert-butyloxy group, 2-chloroethoxy group, 2-chloropropoxy group, 3-chloropropoxy group, 2-chlorobutoxy group, 3-chlorobutoxy group, 4-chlorobutoxy group Etc. can be illustrated.

The alkenyl group having 2 to 4 carbon atoms represented by R ¹ may be linear or branched, and specifically includes a vinyl group, 1-propenyl group, isopropenyl group, 1-butenyl group, 2-butenyl. Examples include groups.

Specific examples of the amino group optionally substituted with an acyl group having 2 to 9 carbon atoms represented by R ¹ include an acetylamino group, a propionylamino group, an isopropionylamino group, a butyrylamino group, and an isobutyrylamino group. Group, pivaloylamino group, hexanoylamino group, octanoylamino group and the like.

The acyl group having 2 to 9 carbon atoms represented by R ¹ may be linear, branched or cyclic, and specifically includes an acetyl group, a propionyl group, an isopropionyl group, a cyclopropanecarbonyl group, and a butyryl group. , Isobutyryl group, cyclobutanecarbonyl group, pivaloyl group, cyclopentanecarbonyl group, hexanoyl group, cyclohexanecarbonyl group, octanoyl group, cyclooctanecarbonyl group and the like.

Further, adjacent R ¹ may be integrated with a carbon atom to be bonded to form an aromatic hydrocarbon ring such as a phenyl group or a naphthyl group.

  Next, the manufacturing method of this invention is demonstrated.

It is essential to carry out the production method of the present invention in the presence of a trimethylphosphine coordinated nickel catalyst. Trimethylphosphine coordinated nickel catalysts that can be used include dichlorobis (trimethylphosphine) nickel, dibromobis (trimethylphosphine) nickel, diiodobis (trimethylphosphine) nickel, benzonitrilebis (trimethylphosphine) nickel, (benzonitrile) (1,5 - cyclooctadiene) bis (trimethylphosphine) nickel, dimethylbis (trimethylphosphine) nickel, propylene bis (trimethylphosphine) nickel, chloro hydride bis (trimethylphosphine) nickel, (eta ³ - allyl) bromo (trimethylphosphine) nickel, (Η ⁵ -cyclopentadienyl) methyl (trimethylphosphine) nickel and the like can be exemplified. From the viewpoint of good yield, dichlorobis (trimethylphosphine) nickel is preferable.

  Nickel such as nickel chloride, nickel bromide, nickel iodide, nickel acetate, nickel nitrate, π-allyl nickel chloride dimer, bis (acetylacetonato) nickel, nickelocene, bis (1,5-cyclooctadiene) nickel The compound and trimethylphosphine may be used in combination to generate a trimethylphosphine coordinated nickel catalyst in the reaction solution. In terms of good yield, the nickel compound is preferably bis (1,5-cyclooctadiene) nickel or nickelocene. The molar ratio of the nickel compound and trimethylphosphine is preferably 1: 0.2 to 1: 5 in terms of a good yield, and more preferably 1: 0.5 to 1: 3.

  Although there is no restriction | limiting in particular in the ratio of the trimethylphosphine coordination nickel catalyst at the time of using for manufacture, and a chlorobenzene derivative (2), 1: 2000-1: 2 are preferable at a point with a sufficient yield, and 1: 200-1: 5 is more preferable.

  In the production method of the present invention, it is essential to carry out in the presence of the alkoxide (4). Alkoxides that can be used include potassium 2,2,2-trifluoroethoxide, rubidium 2,2,2-trifluoroethoxide, cesium 2,2,2-trifluoroethoxide, potassium 2,2-difluoroethoxy , Rubidium 2,2-difluoroethoxide, cesium 2,2-difluoroethoxide, potassium (1,1,1-trifluoro-2-methylpropan-2-yl) oxide, rubidium (1,1,1- Examples thereof include trifluoro-2-methylpropan-2-yl) oxide and cesium (1,1,1-trifluoro-2-methylpropan-2-yl) oxide.

  Further, potassium 2,2,3,3,3-pentafluoropropoxide, rubidium 2,2,3,3,3-pentafluoropropoxide, cesium 2,2,3,3,3-pentafluoropropoxide, Potassium 2,2,3,3,4,4,4-heptafluorobutoxide, rubidium 2,2,3,3,4,4,4-heptafluorobutoxide, cesium 2,2,3,3,4,4 , 4-heptafluorobutoxide, potassium 2,2,3,3,4,4,5,5,5-nonafluoropentyl oxide, rubidium 2,2,3,3,4,4,5,5,5- Nonafluoropentyl oxide, cesium 2,2,3,3,4,4,5,5,5-nonafluoropentyl oxide, potassium 2,2,3,3,4,4,5,5,6,6 6-Undecafluorohexylo Sid, rubidium 2,2,3,3,4,4,5,5,6,6,6-undecafluorohexyl oxide, cesium 2,2,3,3,4,4,5,5,6 Examples thereof include 6,6-undecafluorohexyl oxide.

  Further, potassium 2,2,3,3,4,4,5,5,6,6,7,7,7-tridecafluoroheptyl oxide, rubidium 2,2,3,3,4,4,5 5,6,6,7,7,7-tridecafluoroheptyl oxide, cesium 2,2,3,3,4,4,5,5,6,6,7,7,7-tridecafluoroheptyl oxide , Potassium 2,2,3,3,4,4,5,5,6,6,7,7,8,8,8-pentadecafluorooctyl oxide, rubidium 2,2,3,3,4,4 , 5,5,6,6,7,7,8,8,8-pentadecafluorooctyl oxide, cesium 2,2,3,3,4,4,5,5,6,6,7,7, 8,8,8-pentadecafluorooctyl oxide, potassium 2,2,3,3,4,4,5,5,6,6,7,7,8,8 9,9,9-heptadecafluorononyl oxide, rubidium 2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9,9-heptadecafluoro Nonyl oxide, cesium 2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9,9-heptadecafluorononyl oxide and the like can be exemplified.

  Further, potassium 2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-nonadecafluorodecyl oxide, rubidium 2, 2,3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-nonadecafluorodecyl oxide, cesium 2,2,3,3 , 4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-nonadecafluorodecyl oxide, potassium 2,2,3,3,4,4,4 5,5,6,6,7,7,8,8,9,9,10,10,11,11,11-henicosafluoroundecyl oxide, rubidium 2,2,3,3,4,4 5,5,6,6,7,7,8,8,9,9,10,10,11,11,11-henicosafluoroundecyl oxide, cesium 2,2 3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,11,11,11- Henny Kosa fluoro undecyl oxide and the like.

  In addition, potassium 2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,11,11,12,12,12-tricco Safluorododecyl oxide, rubidium 2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,11,11,12,12, 12-tricosafluorododecyl oxide, cesium 2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,11,11,12 , 12,12-tricosafluorododecyl oxide, potassium 2,2,3,3,4,5,5,6,6,7,7,8,8,9,9,10,10,11, 11, 12, 12, 13, 13, 13-pentacosafluorotridecyl oxide, rubidium 2, 2, 3, 3, 4, 4, 5, 5, 6, 6, , 7,8,8,9,9,10,10,11,11,12,12,13,13,13-pentacosafluorotridecyl oxide, cesium 2,2,3,3,4,4,5 5, 6, 6, 7, 7, 8, 8, 9, 9, 10, 10, 11, 11, 12, 12, 13, 13, 13-pentacosafluorotridecyl oxide and the like.

  Further, potassium 2,2,3,3-tetrafluoropropoxide, rubidium 2,2,3,3-tetrafluoropropoxide, cesium 2,2,3,3-tetrafluoropropoxide, potassium 2,2,3 , 3,4,4-hexafluorobutoxide, rubidium 2,2,3,3,4,4-hexafluorobutoxide, cesium 2,2,3,3,4,4-hexafluorobutoxide, potassium 2,2, 3,3,4,4,5,5-octafluoropentyl oxide, rubidium 2,2,3,3,4,4,5,5-octafluoropentyl oxide, cesium 2,2,3,3,4 4,5,5-octafluoropentyl oxide, potassium 2,2,3,3,4,4,5,5,6,6-decafluorohexyl oxide, rubidium 2,2,3,3,4 , 5,5,6,6- decafluoro hexyl oxide, cesium 2,2,3,3,4,4,5,5,6,6-decafluoro hexyl oxide, and the like can be exemplified.

  Further, potassium 2,2,3,3,4,4,5,5,6,6,7,7-dodecafluoroheptyl oxide, rubidium 2,2,3,3,4,4,5,5,6 , 6,7,7-dodecafluoroheptyl oxide, cesium 2,2,3,3,4,4,5,5,6,6,7,7-dodecafluoroheptyl oxide, potassium 2,2,3,3 , 4,4,5,5,6,6,7,7,8,8-tetradecafluorooctyl oxide, rubidium 2,2,3,3,4,4,5,5,6,6,7, 7,8,8-tetradecafluorooctyl oxide, cesium 2,2,3,3,4,4,5,5,6,6,7,7,8,8-tetradecafluorooctyl oxide, potassium 2, 2,3,3,4,4,5,5,6,6,7,7,8,8,9,9-hexadecafluorono Oxide, rubidium 2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9-hexadecafluorononyl oxide, cesium 2,2,3,3 Examples include 4,4,5,5,6,6,7,7,8,8,9,9-hexadecafluorononyl oxide.

  Further, potassium 2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10-octadecafluoroundecyl oxide, rubidium 2,2 , 3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10-octadecafluoroundecyl oxide, cesium 2,2,3,3,4 4,5,5,6,6,7,7,8,8,9,9,10,10-octadecafluoroundecyl oxide, potassium 2,2,3,3,4,4,5,5 , 6,6,7,7,8,8,9,9,10,10,11,11-eicosafluoroundecyl oxide, rubidium 2,2,3,3,4,4,5,5,6 , 6,7,7,8,8,9,9,10,10,11,11-eicosafluoroundecyl oxide, cesium 2,2,3,3,4 4,5,5,6,6,7,7,8,8,9,9,10,10,11,11- eicosa fluoro undecyl oxide and the like.

  In addition, potassium 2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,11,11,12,12-docosafluorododecyl Oxide, rubidium 2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,11,11,12,12-docosafluorododecyl Oxide, cesium 2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,11,11,12,12-docosafluorododecyl Oxide, potassium 2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,11,11,12,12,13,13 -Tetracosafluorotridecyl oxide, rubidium 2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9,10, 0,11,11,12,12,13,13-tetracosafluorotridecyl oxide, cesium 2,2,3,3,4,4,5,5,6,6,7,7,8,8, Examples include 9, 9, 10, 10, 11, 11, 12, 12, 13, 13-tetracosafluorotridecyl oxide.

  In terms of good yield, potassium 2,2,2-trifluoroethoxide, rubidium 2,2,2-trifluoroethoxide, cesium 2,2,2-trifluoroethoxide, cesium 2,2,3, 3,4,4,5,5,6,6,7,7-dodecafluoroheptyl oxide is preferred.

  The alkoxides (4) can be prepared, for example, by the method described in Chinese Patent Application No. 101318879 or a method analogous thereto.

  The ratio of the alkoxides (4) and the chlorobenzene derivative (2) used in the production is not particularly limited, but is preferably 1: 0.1 to 1:10, and preferably 1: 0.3 in terms of good yield. More preferred is ˜1: 2.

  Alkoxides (4) are 2,2,2-trifluoroethanol, 2,2-difluoroethanol, 1,1,1-trifluoro-2-methylpropan-2-ol, 2,2,3, 3,3-pentafluoropropanol, 2,2,3,3,4,4,4-heptafluorobutanol, 2,2,3,3,3-pentafluoropropanol, 2,2,3,3,4, 4,4-heptafluorobutanol, 2,2,3,3,4,4,5,5,5-nonafluoropentanol, 2,2,3,3,4,4,5,5,6,6 , 6-Undecafluorohexanol, 2,2,3,3,4,4,5,5,6,6,7,7,7-tridecafluoroheptanol, 2,2,3,3,4, 4,5,5,6,6,7,7,8,8,8-pentadecafluorooctanol 2,2,3,3,4,5,5,6,6,7,7,8,8,9,9,9-heptadecafluorononanol, 2,2,3,3,4 4,5,5,6,6,7,7,8,8,9,9,10,10,10-nonadecafluorodecanol, 2,2,3,3,4,4,5,5 6,6,7,7,8,8,9,9,10,10,11,11,11-Henicosafluoroundecanol, 2,2,3,3,4,4,5,5,6 , 6,7,7,8,8,9,9,10,10,11,11,12,12,12-tricosafluorododecanol, 2,2,3,3,4,4,5,5 , 6,6,7,7,8,8,9,9,10,10,11,11,12,12,13,13,13-pentacosafluorotridecanol, 2,2,3,3- Tetrafluoropropanol 2,2,3,3,4,4-hexafluorobutanol, 2,2,3,3,4,4,5,5-octafluoropentanol, 2,2,3,3,4,4,5 , 5,6,6-decafluorohexanol, 2,2,3,3,4,5,5,6,6,7,7-dodecafluoroheptanol, 2,2,3,3,4, 4,5,5,6,6,7,7,8,8-tetradecafluorooctanol, 2,2,3,3,4,5,5,6,6,7,7,8,8 , 9,9-hexadecafluorononanol, 2,2,3,3,4,5,5,6,6,7,7,8,8,9,9,10,10-octadecafluoro Undecanol, 2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,11,11-eicosafluoroundecanol 2 , 2, 3, 3, 4, 4, 5, 5, 6, 6, 7, 7, 8, 8, 9, 9, 10, 10, 11, 11, 12, 12-docosafluorododecanol, 2, 2,3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,11,11,12,12,13,13-tetracosafluorotri It may be generated by reacting an alcohol such as decanol with an alkali metal base in the system.

Alkoxides (4) are trimethyl (2,2,2-trifluoroethoxy) silane, ethyldimethyl (2,2,2-trifluoroethoxy) silane, diethylmethyl (2,2,2-trifluoroethoxy). Silane, triethyl (2,2,2-trifluoroethoxy) silane, tripropyl (2,2,2-trifluoroethoxy) silane, tributyl (2,2,2-trifluoroethoxy) silane, tert-butyldimethyl ( 2,2,2-trifluoroethoxy) silane, (2,2-difluoroethoxy) trimethylsilane, trimethyl [(1,1,1-trifluoro-2-methylpropan-2-yl) oxy] silane, trimethyl ( 2,2,3,3,3-pentafluoropropoxy) silane, (2,2,3,3,4,4,4-hepta Trifluorobutoxy) trimethylsilane, trimethyl (2,2,3,3,4,4,5,5,5-nonafluoropentyloxy) silane, trimethyl (2,2,3,3,4,4,5,5,5) 6,6,6-undecafluorohexyloxy) silane, trimethyl (2,2,3,3,4,4,5,5,6,6,7,7,7-tridecafluoroheptyloxy) silane, Trimethyl (2,2,3,3,4,4,5,5,6,6,7,7,8,8,8-pentadecafluorooctyloxy) silane, (2,2,3,3,4 , 4,5,5,6,6,7,7,8,8,9,9,9-heptadecafluorononyloxy) trimethylsilane, trimethyl (2,2,3,3,4,4,5,5) 5,6,6,7,7,8,8,9,9,10,10,10-nonadecafluorode (Luoxy) silane, (2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,11,11,11-henikosafluoro Undecyloxy) trimethylsilane, trimethyl (2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,11,11,12) , 12,12-tricosafluorododecyloxy) silane, trimethyl (2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10) , 11,11,12,12,13,13,13-pentacosafluorotridecyloxy) silane, trimethyl (2,2,3,3-tetrafluoropropoxy) silane, (2,2,3,3,4) , 4-Hexafluorobutoxy) trimethylsilane, trimethyl (2,2,3,3,4,4,5 , 5-octafluoropentyloxy) silane, (2,2,3,3,4,4,5,5,6,6-decafluorohexyloxy) trimethylsilane, (2,2,3,3,4, 4,5,5,6,6,7,7-dodecafluoroheptyloxy) trimethylsilane, trimethyl (2,2,3,3,4,4,5,5,6,6,7,7,8, 8-tetradecafluorooctyloxy) silane, (2,2,3,3,4,5,5,6,6,7,7,8,8,9,9-hexadecafluorononyloxy) trimethyl Silane, trimethyl (2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10-octadecafluoroundecyloxy) silane, ( 2, 2, 3, 3, 4, 4, 5, 5, 6, 6, 7, 7, 8, 8, 9, 9, 10, 10, 1,11-eicosafluoroundecyloxy) trimethylsilane, (2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10) , 11,11,12,12-docosafluorododecyloxy) trimethylsilane, trimethyl (2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9) , 10, 10, 11, 11, 12, 12, 13, 13-tetracosafluorotridecyloxy) silane and other alkoxy (trialkyl) silanes;
It may be generated by reacting an alkali metal base in the system.

  Specific examples of alkali metal bases that can be used include fluoride salts such as potassium fluoride, rubidium fluoride and cesium fluoride, phosphates such as potassium phosphate and rubidium phosphate, rubidium carbonate and cesium carbonate. And carbonates such as

  In terms of good yield, the alcohols include 2,2,2-trifluoroethanol or 2,2,3,3,4,4,5,5,6,6,7,7-dodecafluoroheptanol. However, as the alkoxy (trialkyl) silanes, trimethyl (2,2,2-trifluoroethoxy) silane is preferable.

  The ratio of these alcohols or alkoxy (trialkyl) silanes to the alkali metal base in use is not particularly limited, but is preferably 1: 0.3 to 1:10 in terms of good yield, and more preferably. Is preferably 1: 0.5 to 1: 5.

  Alkoxy (trialkyl) silanes are prepared from the corresponding trialkylsilyl chlorides and the above alcohols by, for example, the method described in Journal of Fluorine Chemistry, 128, 110-113, 2007, or a method analogous thereto. can do.

  The production method of the present invention can be carried out in an organic solvent, and any organic solvent that does not cause harm to the reaction may be used. Solvents that can be used include ether solvents such as tetrahydrofuran, diethyl ether, cyclopentyl methyl ether, 1,4-dioxane, methyl-tert-butyl ether, 1,2-dimethoxyethane, pentane, xylene, hexane, benzene, toluene. And hydrocarbon solvents such as the above may be exemplified, and two or more of the above solvents may be mixed. From the viewpoint of good yield, ether solvents and hydrocarbon solvents are preferable, and tetrahydrofuran, 1,4-dioxane, toluene and hexane are more preferable.

  The production method of the present invention can be carried out at a temperature appropriately selected from 0 ° C to 200 ° C. The temperature suitably selected from the temperature of 30 degreeC-150 degreeC is a point with a favorable yield.

  The atmosphere during the reaction is preferably an inert gas such as argon or nitrogen, but proceeds sufficiently even in air.

  The method for isolating the phenylboronic acid ester (3) from the solution after the reaction is not particularly limited, but solvent extraction, column chromatography, preparative thin layer chromatography, preparative liquid chromatography, distillation, recrystallization or The object can be obtained by a general method such as sublimation.

  INDUSTRIAL APPLICABILITY The present invention is effective as a method for producing phenyl boronic acid esters useful as a production intermediate for physiologically active substances such as pharmaceuticals and agricultural chemicals, and electronic materials such as liquid crystals and organic EL devices with high yield.

  EXAMPLES Next, although an Example demonstrates this invention in detail, this invention is not limited to these.

  Example-1

アルゴン雰囲気下、反応容器にジクロロビス（トリメチルホスフィン）ニッケル７．０ｍｇ（０．０２５ｍｍｏｌ）、４−クロロアニソール７０．６ｍｇ（０．５ｍｍｏｌ）、フッ化セシウム１５２ｍｇ（１．０ｍｍｏｌ）、４，４，５，５，４’，４’，５’，５’−オクタメチル−２，２’−ビ（１，３，２−ジオキサボロラニル）１４０ｍｇ（０．５５ｍｍｏｌ）、トリメチル（２，２，２−トリフルオロエトキシ）シラン１８０ｍｇ（１．０５ｍｍｏｌ）およびテトラヒドロフラン０．５ｍＬを加えて密閉し、１００℃で２時間攪拌した。反応容器を室温まで冷却した後、飽和塩化アンモニウム水溶液１ｍＬを加え酢酸エチル８ｍＬで３回抽出した。得られた有機相を、ガスクロマトグラフィーを用いて分析することにより、目的物の生成を確認した（ＧＣ収率９７％）。溶媒を減圧留去し、残渣をシリカゲルカラムクロマトグラフィ（ヘキサン：クロロホルム：酢酸エチル＝１６：４：０〜１６：４：１）を用いて精製することにより、２−（４−メトキシフェニル）−４，４，５，５−テトラメチル−１，３，２−ジオキサボロラン１０７ｍｇ（無色液体、収率９３％）を得た。
^１Ｈ−ＮＭＲ（ＣＤＣｌ_３，４００ＭＨｚ）δ７．７５（ｄ，Ｊ＝８．６Ｈｚ，２Ｈ），６．８９（ｄ，Ｊ＝８．６Ｈｚ，２Ｈ），３．８１（ｓ，３Ｈ），１．３３（ｓ，１２Ｈ）。

Under argon atmosphere, dichlorobis (trimethylphosphine) nickel 7.0 mg (0.025 mmol), 4-chloroanisole 70.6 mg (0.5 mmol), cesium fluoride 152 mg (1.0 mmol), 4, 4, 5 , 5,4 ′, 4 ′, 5 ′, 5′-octamethyl-2,2′-bi (1,3,2-dioxaborolanyl) 140 mg (0.55 mmol), trimethyl (2,2,2) -Trifluoroethoxy) silane (180 mg, 1.05 mmol) and tetrahydrofuran (0.5 mL) were added and sealed, followed by stirring at 100 ° C. for 2 hours. After cooling the reaction vessel to room temperature, 1 mL of saturated aqueous ammonium chloride solution was added, and the mixture was extracted 3 times with 8 mL of ethyl acetate. The resulting organic phase was analyzed using gas chromatography to confirm the production of the target product (GC yield 97%). The solvent was distilled off under reduced pressure, and the residue was purified using silica gel column chromatography (hexane: chloroform: ethyl acetate = 16: 4: 0 to 16: 4: 1) to give 2- (4-methoxyphenyl) -4. , 4,5,5-tetramethyl-1,3,2-dioxaborolane (107 mg, colorless liquid, yield 93%).
¹ H-NMR (CDCl ₃ , 400 MHz) δ 7.75 (d, J = 8.6 Hz, 2H), 6.89 (d, J = 8.6 Hz, 2H), 3.81 (s, 3H), 1 .33 (s, 12H).

Example-2
424 mg of trimethyl (2,2,3,3,4,4,5,5,6,7,7-dodecafluoroheptyloxy) silane instead of trimethyl (2,2,2-trifluoroethoxy) silane Except for using 1.05 mmol), the same operation as in Example 1 was performed, and analysis using gas chromatography confirmed the generation of the target product (GC yield 95%).

Example-3
Under an argon atmosphere, 4.2 mg (0.015 mmol) of dichlorobis (trimethylphosphine) nickel, 70.6 mg (0.5 mol) of 4-chloroanisole, 152 mg (1.0 mmol) of cesium fluoride, 4, 4, 5 , 5,4 ′, 4 ′, 5 ′, 5′-octamethyl-2,2′-bi (1,3,2-dioxaborolanyl) 140 mg (0.55 mmol), trimethyl (2,2,2) -Trifluoroethoxy) silane (180 mg, 1.05 mmol) and tetrahydrofuran (0.5 mL) were added and sealed, followed by stirring at 100 ° C. for 12 hours. After cooling the reaction vessel to room temperature, 1 mL of a saturated aqueous ammonium chloride solution and 8 mL of ethyl acetate were added, and then analyzed by gas chromatography to obtain 2- (4-methoxyphenyl) -4, 4, 5, 5 -Formation of tetramethyl-1,3,2-dioxaborolane was confirmed (GC yield 98%).

Example-4
Except for using 212 mg (1.0 mmol) of potassium phosphate in place of cesium fluoride, the same operation as in Example 3 was carried out, and analysis using gas chromatography confirmed the production of the target product ( GC yield 78%).

Comparative Example-1
By performing the same operation as in Example 3 except that 9.8 mg (0.015 mmol) of dichlorobis (triphenylphosphine) nickel was used instead of dichlorobis (trimethylphosphine) nickel, and analyzing using gas chromatography The formation of the target product was confirmed (GC yield 49%).

Example-5
Gas chromatography was performed in the same manner as in Example 3 except that 162 mg (1.05 mmol) of (2,2-difluoroethoxy) trimethylsilane was used instead of trimethyl (2,2,2-trifluoroethoxy) silane. The formation of the target product was confirmed by analysis using a graph (GC yield 97%).

Example-6
Other than using 210 mg (1.05 mmol) of [(1,1,1-trifluoro-2-methylpropan-2-yl) oxy] trimethylsilane instead of trimethyl (2,2,2-trifluoroethoxy) silane Were all subjected to the same operation as in Example 3 and analyzed by gas chromatography, thereby confirming the production of the target product (GC yield 87%).

Example-7
Except that 104 mg (1.0 mmol) of rubidium fluoride was used instead of cesium fluoride, the same operation as in Example 3 was performed, and analysis using gas chromatography confirmed the production of the target product ( GC yield 87%).

Example-8
Except that 58.1 mg (1.0 mmol) of potassium fluoride was used instead of cesium fluoride and 0.5 mL of 1,4-dioxane was used instead of tetrahydrofuran, all the same operations as in Example-3 were performed, and gas chromatography was performed. By using and analyzing, the production | generation of the target object was confirmed (GC yield 90%).

  Example-9

アルゴン雰囲気下、反応容器にジクロロビス（トリメチルホスフィン）ニッケル１４．０ｍｇ（０．０５ｍｍｏｌ）、４−クロロアニソール７０．６ｍｇ（０．５ｍｍｏｌ）、カリウム２，２，２−トリフルオロエトキシド１３８ｍｇ（１．０ｍｍｏｌ）、４，４，５，５，４’，４’，５’，５’−オクタメチル−２，２’−ビ（１，３，２−ジオキサボロラニル）１４０ｍｇ（０．５５ｍｍｏｌ）およびトルエン０．５ｍＬを加えて密閉し、１００℃で１２時間攪拌した。反応容器を室温まで冷却した後、飽和塩化アンモニウム水溶液１ｍＬを加え酢酸エチル８ｍＬで３回抽出した。得られた有機相を、ガスクロマトグラフィーを用いて分析することにより、目的物の生成を確認した（ＧＣ収率８６％）。溶媒を減圧留去し、残渣をシリカゲルカラムクロマトグラフィ（ヘキサン：クロロホルム：酢酸エチル＝１６：４：０〜１６：４：１）を用いて精製することにより、２−（４−メトキシフェニル）−４，４，５，５−テトラメチル−１，３，２−ジオキサボロラン９３ｍｇ（無色液体、収率７９％）を得た。

Under an argon atmosphere, 14.0 mg (0.05 mmol) of dichlorobis (trimethylphosphine) nickel, 70.6 mg (0.5 mmol) of 4-chloroanisole, 138 mg of potassium 2,2,2-trifluoroethoxide (1. 0 mmol), 4,4,5,5,4 ′, 4 ′, 5 ′, 5′-octamethyl-2,2′-bi (1,3,2-dioxaborolanyl) 140 mg (0.55 mmol) Then, 0.5 mL of toluene was added and sealed, followed by stirring at 100 ° C. for 12 hours. After cooling the reaction vessel to room temperature, 1 mL of saturated aqueous ammonium chloride solution was added, and the mixture was extracted 3 times with 8 mL of ethyl acetate. The obtained organic phase was analyzed using gas chromatography to confirm the production of the target product (GC yield 86%). The solvent was distilled off under reduced pressure, and the residue was purified using silica gel column chromatography (hexane: chloroform: ethyl acetate = 16: 4: 0 to 16: 4: 1) to give 2- (4-methoxyphenyl) -4. , 4,5,5-tetramethyl-1,3,2-dioxaborolane (93 mg, colorless liquid, yield 79%) was obtained.

Comparative Example-2
By performing the same operation as in Example-9 except that 153 mg (1.5 mmol) of triethylamine was used in place of potassium 2,2,2-trifluoroethoxide, the target product was analyzed by gas chromatography. The generation of could not be confirmed.

  Example-10

アルゴン雰囲気下、反応容器にジクロロビス（トリメチルホスフィン）ニッケル１．４ｍｇ（０．００５ｍｍｏｌ）、４−クロロ安息香酸メチル８５．０ｍｇ（０．５ｍｍｏｌ）、フッ化セシウム１５２ｍｇ（１．０ｍｍｏｌ）、４，４，５，５，４’，４’，５’，５’−オクタメチル−２，２’−ビ（１，３，２−ジオキサボロラニル）１４０ｍｇ（０．５５ｍｍｏｌ）、トリメチル（２，２，２−トリフルオロエトキシ）シラン１８０ｍｇ（１．０５ｍｍｏｌ）およびテトラヒドロフラン０．５ｍＬを加えて密閉し、１００℃で１２時間攪拌した。反応容器を室温まで冷却した後、飽和塩化アンモニウム水溶液１ｍＬを加え酢酸エチル８ｍＬで３回抽出し、得られた有機相を合わせた。溶媒を減圧留去し、残渣をシリカゲルカラムクロマトグラフィ（ヘキサン：クロロホルム：酢酸エチル＝１６：４：０〜１６：４：１）を用いて精製することにより、４−（４，４，５，５−テトラメチル−１，３，２−ジオキサボロラン−２−イル）安息香酸メチル１２９ｍｇ（白色固体、収率９９％）を得た。
^１Ｈ−ＮＭＲ（ＣＤＣｌ_３，４００ＭＨｚ）δ８．０２（ｄ，Ｊ＝８．３Ｈｚ，２Ｈ），７．８７（ｄ，Ｊ＝８．３Ｈｚ，２Ｈ），３．９２（ｓ，３Ｈ），１．３６（ｓ，１２Ｈ）。

Under argon atmosphere, dichlorobis (trimethylphosphine) nickel 1.4 mg (0.005 mmol), methyl 4-chlorobenzoate 85.0 mg (0.5 mmol), cesium fluoride 152 mg (1.0 mmol), 4,4 , 5,5,4 ′, 4 ′, 5 ′, 5′-octamethyl-2,2′-bi (1,3,2-dioxaborolanyl) 140 mg (0.55 mmol), trimethyl (2,2 , 2-trifluoroethoxy) silane (180 mg, 1.05 mmol) and tetrahydrofuran (0.5 mL) were added, and the mixture was sealed and stirred at 100 ° C. for 12 hr. After the reaction vessel was cooled to room temperature, 1 mL of a saturated aqueous ammonium chloride solution was added, followed by extraction three times with 8 mL of ethyl acetate, and the resulting organic phases were combined. The solvent was distilled off under reduced pressure, and the residue was purified by silica gel column chromatography (hexane: chloroform: ethyl acetate = 16: 4: 0 to 16: 4: 1) to give 4- (4, 4, 5, 5 129 mg (white solid, yield 99%) of methyl tetramethyl-1,3,2-dioxaborolan-2-yl) benzoate were obtained.
¹ H-NMR (CDCl ₃ , 400 MHz) δ 8.02 (d, J = 8.3 Hz, 2H), 7.87 (d, J = 8.3 Hz, 2H), 3.92 (s, 3H), 1 .36 (s, 12H).

Example-11
The same operation as in Example-10 was carried out except that 0.5 mL of toluene was used instead of tetrahydrofuran, and 4- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) was used. Obtained 119 mg of methyl benzoate (white solid, 90% yield).

Example-12
Under argon atmosphere, dichlorobis (trimethylphosphine) nickel 1.4 mg (0.005 mmol), methyl 4-chlorobenzoate 85.0 mg (0.5 mmol), potassium 2,2,2-trifluoroethoxide 138 mg ( 1.0 mmol), 4,4,5,5,4 ′, 4 ′, 5 ′, 5′-octamethyl-2,2′-bi (1,3,2-dioxaborolanyl) 140 mg (0. 55 mmol) and 0.5 mL of toluene were added and sealed, followed by stirring at 100 ° C. for 12 hours. After cooling the reaction vessel to room temperature, 1 mL of a saturated aqueous ammonium chloride solution and 8 mL of ethyl acetate were added, and then analyzed by gas chromatography to obtain 4- (4,4,5,5-tetramethyl-1, Formation of methyl 3,2-dioxaborolan-2-yl) benzoate was confirmed (GC yield 88%).

Comparative Example-3
By performing the same operation as in Example-12 except that 32.7 mg (0.05 mmol) of dichlorobis (triphenylphosphine) nickel was used instead of dichlorobis (trimethylphosphine) nickel, and analyzing by gas chromatography The formation of the target product was confirmed (GC yield 42%).

Comparative Example-4
Except for using 34.2 mg (0.05 mmol) of dichloro [1,1′-bis (diphenylphosphino) ferrocene] nickel instead of dichlorobis (trimethylphosphine) nickel, the same operation as in Example-12 was carried out. The formation of the target product was confirmed by analysis using chromatography (GC yield 35%).

Comparative Example-5
Gas chromatography was performed in the same manner as in Example-12 except that 27.1 mg (0.05 mmol) of dichloro [1,3-bis (diphenylphosphino) propane] nickel was used instead of dichlorobis (trimethylphosphine) nickel. The formation of the target product was confirmed by analysis using a graph (GC yield 31%).

Comparative Example-6
By performing the same operation as in Example-12 except that 34.5 mg (0.05 mmol) of dichlorobis (tricyclohexylphosphine) nickel was used instead of dichlorobis (trimethylphosphine) nickel, and analyzing by gas chromatography The formation of the target product was confirmed (GC yield 49%).

Example-13
Example -12 except that bis (1,5-cyclooctadiene) nickel 1.4 mg (0.005 mmol) and trimethylphosphine 0.8 mg (0.01 mmol) were used instead of dichlorobis (trimethylphosphine) nickel. By performing the same operation and analyzing using gas chromatography, the production of the target product was confirmed (GC yield 92%).

Example-14
Except for using nickelocene 0.9 mg (0.005 mmol) and trimethylphosphine 0.8 mg (0.01 mmol) in place of dichlorobis (trimethylphosphine) nickel, all the same operations as in Example-12 were performed, and gas chromatography was used. Analysis to confirm the formation of the desired product (GC yield 74%).

Example-15
Under argon atmosphere, dichlorobis (trimethylphosphine) nickel 1.4 mg (0.005 mmol), methyl 4-chlorobenzoate 85.0 mg (0.5 mmol), potassium 2,2,2-trifluoroethoxide 138 mg ( 1.0 mmol), 4,4,5,5,4 ′, 4 ′, 5 ′, 5′-octamethyl-2,2′-bi (1,3,2-dioxaborolanyl) 140 mg (0. 55 mmol) and hexane 0.5 mL were added and sealed, followed by stirring at 100 ° C. for 12 hours. After the reaction vessel was cooled to room temperature, 1 mL of a saturated aqueous ammonium chloride solution was added, followed by extraction three times with 8 mL of ethyl acetate, and the resulting organic phases were combined. The solvent was distilled off under reduced pressure, and the residue was purified by silica gel column chromatography (hexane: chloroform: ethyl acetate = 16: 4: 0 to 16: 4: 1) to give 4- (4, 4, 5, 5 105 mg (white solid, yield 79%) of methyl tetramethyl-1,3,2-dioxaborolan-2-yl) benzoate were obtained.

  Example-16

アルゴン雰囲気下、反応容器にジクロロビス（トリメチルホスフィン）ニッケル１４．０ｍｇ（０．０５ｍｍｏｌ）、２−クロロアニソール７１．０ｍｇ（０．５ｍｍｏｌ）、カリウム２，２，２−トリフルオロエトキシド１３８ｍｇ（１．０ｍｍｏｌ）、４，４，５，５，４’，４’，５’，５’−オクタメチル−２，２’−ビ（１，３，２−ジオキサボロラニル）１６５ｍｇ（０．６５ｍｍｏｌ）およびトルエン０．５ｍＬを加えて密閉し、１００℃で１２時間攪拌した。反応容器を室温まで冷却した後、飽和塩化アンモニウム水溶液１ｍＬを加え酢酸エチル８ｍＬで３回抽出し、得られた有機相を合わせた。溶媒を減圧留去し、残渣をシリカゲルカラムクロマトグラフィ（ヘキサン：クロロホルム：酢酸エチル＝１６：４：０〜１６：４：１）を用いて精製することにより、２−（２−メトキシフェニル）−４，４，５，５−テトラメチル−１，３，２−ジオキサボロラン８９ｍｇ（白色固体、収率７６％）を得た。
^１Ｈ−ＮＭＲ（ＣＤＣｌ_３，４００ＭＨｚ）δ７．６８（ｄｄ，Ｊ＝１．８Ｈｚ，７．３Ｈｚ，１Ｈ），７．３９（ｄｄｄ，Ｊ＝１．８Ｈｚ，７．３Ｈｚ，８．３Ｈｚ，１Ｈ），６．９４（ｄｄ，Ｊ＝７．３Ｈｚ，７．３Ｈｚ，１Ｈ），６．８５（ｄ，Ｊ＝８．３Ｈｚ，１Ｈ），３．８３（ｓ，３Ｈ），１．３５（ｓ，１２Ｈ）。

Under an argon atmosphere, 14.0 mg (0.05 mmol) of dichlorobis (trimethylphosphine) nickel, 71.0 mg (0.5 mmol) of 2-chloroanisole, 138 mg of potassium 2,2,2-trifluoroethoxide (1. 0 mmol), 4,4,5,5,4 ′, 4 ′, 5 ′, 5′-octamethyl-2,2′-bi (1,3,2-dioxaborolanyl) 165 mg (0.65 mmol) Then, 0.5 mL of toluene was added and sealed, followed by stirring at 100 ° C. for 12 hours. After the reaction vessel was cooled to room temperature, 1 mL of a saturated aqueous ammonium chloride solution was added, followed by extraction three times with 8 mL of ethyl acetate, and the resulting organic phases were combined. The solvent was distilled off under reduced pressure, and the residue was purified using silica gel column chromatography (hexane: chloroform: ethyl acetate = 16: 4: 0 to 16: 4: 1) to give 2- (2-methoxyphenyl) -4. , 4,5,5-tetramethyl-1,3,2-dioxaborolane (white solid, yield 76%).
¹ H-NMR (CDCl ₃ , 400 MHz) δ 7.68 (dd, J = 1.8 Hz, 7.3 Hz, 1H), 7.39 (ddd, J = 1.8 Hz, 7.3 Hz, 8.3 Hz, 1H) ), 6.94 (dd, J = 7.3 Hz, 7.3 Hz, 1H), 6.85 (d, J = 8.3 Hz, 1H), 3.83 (s, 3H), 1.35 (s) , 12H).

  Example-17

アルゴン雰囲気下、反応容器にジクロロビス（トリメチルホスフィン）ニッケル２．８ｍｇ（０．０１ｍｍｏｌ）、３−クロロアニソール７０．７ｍｇ（０．５ｍｍｏｌ）、フッ化セシウム１５２ｍｇ（１．０ｍｍｏｌ）、４，４，５，５，４’，４’，５’，５’−オクタメチル−２，２’−ビ（１，３，２−ジオキサボロラニル）１４０ｍｇ（０．５５ｍｍｏｌ）、トリメチル（２，２，２−トリフルオロエトキシ）シラン１８０ｍｇ（１．０５ｍｍｏｌ）およびテトラヒドロフラン０．５ｍＬを加えて密閉し、１００℃で１２時間攪拌した。反応容器を室温まで冷却した後、飽和塩化アンモニウム水溶液１ｍＬを加え酢酸エチル８ｍＬで３回抽出し、得られた有機相を合わせた。溶媒を減圧留去し、残渣をシリカゲルカラムクロマトグラフィ（ヘキサン：クロロホルム：酢酸エチル＝１６：４：０〜１６：４：１）を用いて精製することにより、２−（３−メトキシフェニル）−４，４，５，５−テトラメチル−１，３，２−ジオキサボロラン９４ｍｇ（無色液体、収率８１％）を得た。
^１Ｈ−ＮＭＲ（ＣＤＣｌ_３，４００ＭＨｚ）δ７．４０（ｄｄ，Ｊ＝０．９Ｈｚ，７．２Ｈｚ，１Ｈ），７．３３−７．２７（ｍ，２Ｈ），７．００（ｄｄｄ，Ｊ＝０．９Ｈｚ，１．８Ｈｚ，８．２Ｈｚ，１Ｈ），３．８２（ｓ，３Ｈ），１．３４（ｓ，１２Ｈ）。

Under an argon atmosphere, 2.8 mg (0.01 mmol) of dichlorobis (trimethylphosphine) nickel, 70.7 mg (0.5 mmol) of 3-chloroanisole, 152 mg (1.0 mmol) of cesium fluoride, 4, 4, 5 , 5,4 ′, 4 ′, 5 ′, 5′-octamethyl-2,2′-bi (1,3,2-dioxaborolanyl) 140 mg (0.55 mmol), trimethyl (2,2,2) -Trifluoroethoxy) silane (180 mg, 1.05 mmol) and tetrahydrofuran (0.5 mL) were added and sealed, followed by stirring at 100 ° C. for 12 hours. After the reaction vessel was cooled to room temperature, 1 mL of a saturated aqueous ammonium chloride solution was added, followed by extraction three times with 8 mL of ethyl acetate, and the resulting organic phases were combined. The solvent was distilled off under reduced pressure, and the residue was purified using silica gel column chromatography (hexane: chloroform: ethyl acetate = 16: 4: 0 to 16: 4: 1) to give 2- (3-methoxyphenyl) -4. , 4,5,5-tetramethyl-1,3,2-dioxaborolane (94 mg, colorless liquid, 81% yield).
¹ H-NMR (CDCl ₃ , 400 MHz) δ 7.40 (dd, J = 0.9 Hz, 7.2 Hz, 1H), 7.33-7.27 (m, 2H), 7.00 (ddd, J = 0.9 Hz, 1.8 Hz, 8.2 Hz, 1H), 3.82 (s, 3H), 1.34 (s, 12H).

  Example-18

アルゴン雰囲気下、反応容器にジクロロビス（トリメチルホスフィン）ニッケル４．２ｍｇ（０．０１５ｍｍｏｌ）、４−ｔｅｒｔ−ブトキシ−１−クロロベンゼン９１．８ｍｇ（０．５ｍｍｏｌ）、フッ化セシウム１５２ｍｇ（１．０ｍｍｏｌ）、４，４，５，５，４’，４’，５’，５’−オクタメチル−２，２’−ビ（１，３，２−ジオキサボロラニル）１４０ｍｇ（０．５５ｍｍｏｌ）、トリメチル（２，２，２−トリフルオロエトキシ）シラン１８０ｍｇ（１．０５ｍｍｏｌ）およびテトラヒドロフラン０．５ｍＬを加えて密閉し、１００℃で１２時間攪拌した。反応容器を室温まで冷却した後、飽和塩化アンモニウム水溶液１ｍＬを加え酢酸エチル８ｍＬで３回抽出し、得られた有機相を合わせた。溶媒を減圧留去し、残渣をシリカゲルカラムクロマトグラフィ（ヘキサン：クロロホルム：酢酸エチル＝１６：４：０〜１６：４：１）を用いて精製することにより、２−（４−ｔｅｒｔ−ブトキシフェニル）−４，４，５，５−テトラメチル−１，３，２−ジオキサボロラン１１５ｍｇ（白色固体、収率８４％）を得た。
^１Ｈ−ＮＭＲ（ＣＤＣｌ_３，４００ＭＨｚ）δ７．７２（ｄ，Ｊ＝８．４Ｈｚ，２Ｈ），６．９９（ｄ，Ｊ＝８．４Ｈｚ，２Ｈ），１．３６（ｓ，９Ｈ），１．３３（ｓ，１２Ｈ）。

Under argon atmosphere, 4.2 mg (0.015 mmol) of dichlorobis (trimethylphosphine) nickel, 91.8 mg (0.5 mmol) of 4-tert-butoxy-1-chlorobenzene, 152 mg (1.0 mmol) of cesium fluoride, 4,4,5,5,4 ′, 4 ′, 5 ′, 5′-octamethyl-2,2′-bi (1,3,2-dioxaborolanyl) 140 mg (0.55 mmol), trimethyl ( 180 mg (1.05 mmol) of 2,2,2-trifluoroethoxy) silane and 0.5 mL of tetrahydrofuran were added and sealed, and the mixture was stirred at 100 ° C. for 12 hours. After the reaction vessel was cooled to room temperature, 1 mL of a saturated aqueous ammonium chloride solution was added, followed by extraction three times with 8 mL of ethyl acetate, and the resulting organic phases were combined. The solvent was distilled off under reduced pressure, and the residue was purified using silica gel column chromatography (hexane: chloroform: ethyl acetate = 16: 4: 0 to 16: 4: 1) to give 2- (4-tert-butoxyphenyl). 115 mg of -4,4,5,5-tetramethyl-1,3,2-dioxaborolane (white solid, 84% yield) was obtained.
¹ H-NMR (CDCl ₃ , 400 MHz) δ 7.72 (d, J = 8.4 Hz, 2H), 6.99 (d, J = 8.4 Hz, 2H), 1.36 (s, 9H), 1 .33 (s, 12H).

  Example-19

アルゴン雰囲気下、反応容器にジクロロビス（トリメチルホスフィン）ニッケル４．２ｍｇ（０．０１５ｍｍｏｌ）、１−クロロ−４−（４−クロロブトキシ）ベンゼン１１０ｍｇ（０．５ｍｍｏｌ）、フッ化セシウム１５２ｍｇ（１．０ｍｍｏｌ）、４，４，５，５，４’，４’，５’，５’−オクタメチル−２，２’−ビ（１，３，２−ジオキサボロラニル）１４０ｍｇ（０．５５ｍｍｏｌ）、トリメチル（２，２，２−トリフルオロエトキシ）シラン１８０ｍｇ（１．０５ｍｍｏｌ）およびテトラヒドロフラン０．５ｍＬを加えて密閉し、１００℃で１２時間攪拌した。反応容器を室温まで冷却した後、飽和塩化アンモニウム水溶液１ｍＬを加え酢酸エチル８ｍＬで３回抽出し、得られた有機相を合わせた。溶媒を減圧留去し、残渣をシリカゲルカラムクロマトグラフィ（ヘキサン：クロロホルム：酢酸エチル＝１６：４：０〜１６：４：１）を用いて精製することにより、２−［４−（４−クロロブトキシ）フェニル］−４，４，５，５−テトラメチル−１，３，２−ジオキサボロラン１２２ｍｇ（無色液体、収率７８％）を得た。
^１Ｈ−ＮＭＲ（ＣＤＣｌ_３，４００ＭＨｚ）δ７．７４（ｄ，Ｊ＝８．７Ｈｚ，２Ｈ），６．８８（ｄ，Ｊ＝８．７Ｈｚ，２Ｈ），４．０２（ｔ，Ｊ＝５．８Ｈｚ，２Ｈ），３．６２（ｔ，Ｊ＝６．２Ｈｚ，２Ｈ），２．０２−１．９１（ｍ，４Ｈ），１．３３（ｓ，１２Ｈ）。

Under an argon atmosphere, dichlorobis (trimethylphosphine) nickel 4.2 mg (0.015 mmol), 1-chloro-4- (4-chlorobutoxy) benzene 110 mg (0.5 mmol), cesium fluoride 152 mg (1.0 mmol) ), 4,4,5,5,4 ′, 4 ′, 5 ′, 5′-octamethyl-2,2′-bi (1,3,2-dioxaborolanyl) 140 mg (0.55 mmol), 180 mg (1.05 mmol) of trimethyl (2,2,2-trifluoroethoxy) silane and 0.5 mL of tetrahydrofuran were added and sealed, followed by stirring at 100 ° C. for 12 hours. After the reaction vessel was cooled to room temperature, 1 mL of a saturated aqueous ammonium chloride solution was added, followed by extraction three times with 8 mL of ethyl acetate, and the resulting organic phases were combined. The solvent was distilled off under reduced pressure, and the residue was purified by silica gel column chromatography (hexane: chloroform: ethyl acetate = 16: 4: 0 to 16: 4: 1) to give 2- [4- (4-chlorobutoxy). ) Phenyl] -4,4,5,5-tetramethyl-1,3,2-dioxaborolane (122 mg, colorless liquid, yield 78%).
¹ H-NMR (CDCl ₃ , 400 MHz) δ 7.74 (d, J = 8.7 Hz, 2H), 6.88 (d, J = 8.7 Hz, 2H), 4.02 (t, J = 5. 8 Hz, 2H), 3.62 (t, J = 6.2 Hz, 2H), 2.02-1.91 (m, 4H), 1.33 (s, 12H).

  Example-20

アルゴン雰囲気下、反応容器にジクロロビス（トリメチルホスフィン）ニッケル７．０ｍｇ（０．０２５ｍｍｏｌ）、２−クロロ安息香酸エチル９１．４ｍｇ（０．５ｍｍｏｌ）、フッ化セシウム１５２ｍｇ（１．０ｍｍｏｌ）、４，４，５，５，４’，４’，５’，５’−オクタメチル−２，２’−ビ（１，３，２−ジオキサボロラニル）１４０ｍｇ（０．５５ｍｍｏｌ）、トリメチル（２，２，２−トリフルオロエトキシ）シラン１８０ｍｇ（１．０５ｍｍｏｌ）およびテトラヒドロフラン０．５ｍＬを加えて密閉し、１００℃で２時間攪拌した。反応容器を室温まで冷却した後、飽和塩化アンモニウム水溶液１ｍＬを加え酢酸エチル８ｍＬで３回抽出し、得られた有機相を合わせた。溶媒を減圧留去し、残渣をシリカゲルカラムクロマトグラフィ（ヘキサン：クロロホルム：酢酸エチル＝１６：４：０〜１６：４：１）を用いて精製することにより、２−（４，４，５，５−テトラメチル−１，３，２−ジオキサボロラン−２−イル）安息香酸エチル１０７ｍｇ（白色固体、収率７８％）を得た。
^１Ｈ−ＮＭＲ（ＣＤＣｌ_３，４００ＭＨｚ）δ７．９３（ｄｄｄ，Ｊ＝０．８Ｈｚ，０．８Ｈｚ，７．８Ｈｚ，１Ｈ），７．５１−７．４８（ｍ，２Ｈ），７．４０（ｄｄｄ，Ｊ＝３．４Ｈｚ，５．３Ｈｚ，７．８Ｈｚ，１Ｈ），４．３８（ｑ，Ｊ＝７．２Ｈｚ，２Ｈ），１．４２（ｓ，１２Ｈ），１．３８（ｔ，Ｊ＝７．２Ｈｚ，３Ｈ）。

Under argon atmosphere, 7.0 mg (0.025 mmol) of dichlorobis (trimethylphosphine) nickel, 91.4 mg (0.5 mmol) of ethyl 2-chlorobenzoate, 152 mg (1.0 mmol) of cesium fluoride, 4,4 , 5,5,4 ′, 4 ′, 5 ′, 5′-octamethyl-2,2′-bi (1,3,2-dioxaborolanyl) 140 mg (0.55 mmol), trimethyl (2,2 , 2-trifluoroethoxy) silane (180 mg, 1.05 mmol) and tetrahydrofuran (0.5 mL) were added, and the mixture was sealed and stirred at 100 ° C. for 2 hr. After the reaction vessel was cooled to room temperature, 1 mL of a saturated aqueous ammonium chloride solution was added, followed by extraction three times with 8 mL of ethyl acetate, and the resulting organic phases were combined. The solvent was distilled off under reduced pressure, and the residue was purified by silica gel column chromatography (hexane: chloroform: ethyl acetate = 16: 4: 0 to 16: 4: 1) to give 2- (4, 4, 5, 5 107 mg (white solid, yield 78%) of ethyl tetramethyl-1,3,2-dioxaborolan-2-yl) benzoate were obtained.
¹ H-NMR (CDCl ₃ , 400 MHz) δ 7.93 (ddd, J = 0.8 Hz, 0.8 Hz, 7.8 Hz, 1 H), 7.51-7.48 (m, 2H), 7.40 ( ddd, J = 3.4 Hz, 5.3 Hz, 7.8 Hz, 1H), 4.38 (q, J = 7.2 Hz, 2H), 1.42 (s, 12H), 1.38 (t, J = 7.2 Hz, 3H).

  Example-21

アルゴン雰囲気下、反応容器にジクロロビス（トリメチルホスフィン）ニッケル２．８ｍｇ（０．０１ｍｍｏｌ）、（４−クロロフェニル）メチルケトン７６．５ｍｇ（０．５ｍｍｏｌ）、フッ化セシウム１５２ｍｇ（１．０ｍｍｏｌ）、４，４，５，５，４’，４’，５’，５’−オクタメチル−２，２’−ビ（１，３，２−ジオキサボロラニル）１４０ｍｇ（０．５５ｍｍｏｌ）、トリメチル（２，２，２−トリフルオロエトキシ）シラン１８０ｍｇ（１．０５ｍｍｏｌ）およびテトラヒドロフラン０．５ｍＬを加えて密閉し、１００℃で１２時間攪拌した。反応容器を室温まで冷却した後、飽和塩化アンモニウム水溶液１ｍＬを加え酢酸エチル８ｍＬで３回抽出し、得られた有機相を合わせた。溶媒を減圧留去し、残渣をシリカゲルカラムクロマトグラフィ（ヘキサン：クロロホルム：酢酸エチル＝１６：４：０〜１６：４：１）を用いて精製することにより、メチル［４−（４，４，５，５−テトラメチル−１，３，２−ジオキサボロラン−２−イル）フェニル］ケトン９９ｍｇ（白色固体、収率８１％）を得た。
^１Ｈ−ＮＭＲ（ＣＤＣｌ_３，４００ＭＨｚ）δ７．９３（ｄ，Ｊ＝８．４Ｈｚ，２Ｈ），７．８９（ｄ，Ｊ＝８．４Ｈｚ，２Ｈ），２．６２（ｓ，３Ｈ），１．３６（ｓ，１２Ｈ）。

Under an argon atmosphere, 2.8 mg (0.01 mmol) of dichlorobis (trimethylphosphine) nickel, 76.5 mg (0.5 mmol) of (4-chlorophenyl) methylketone, 152 mg (1.0 mmol) of cesium fluoride, 4,4 , 5,5,4 ′, 4 ′, 5 ′, 5′-octamethyl-2,2′-bi (1,3,2-dioxaborolanyl) 140 mg (0.55 mmol), trimethyl (2,2 , 2-trifluoroethoxy) silane (180 mg, 1.05 mmol) and tetrahydrofuran (0.5 mL) were added, and the mixture was sealed and stirred at 100 ° C. for 12 hr. After the reaction vessel was cooled to room temperature, 1 mL of a saturated aqueous ammonium chloride solution was added, followed by extraction three times with 8 mL of ethyl acetate, and the resulting organic phases were combined. The solvent was distilled off under reduced pressure, and the residue was purified by silica gel column chromatography (hexane: chloroform: ethyl acetate = 16: 4: 0 to 16: 4: 1) to give methyl [4- (4,4,5 , 5-tetramethyl-1,3,2-dioxaborolan-2-yl) phenyl] ketone 99 mg (white solid, 81% yield) was obtained.
¹ H-NMR (CDCl ₃ , 400 MHz) δ 7.93 (d, J = 8.4 Hz, 2H), 7.89 (d, J = 8.4 Hz, 2H), 2.62 (s, 3H), 1 .36 (s, 12H).

  Example-22

アルゴン雰囲気下、反応容器にジクロロビス（トリメチルホスフィン）ニッケル１．４ｍｇ（０．００５ｍｍｏｌ）、（４−クロロフェニル）フェニルケトン１０８ｍｇ（０．５ｍｍｏｌ）、フッ化セシウム１５２ｍｇ（１．０ｍｍｏｌ）、４，４，５，５，４’，４’，５’，５’−オクタメチル−２，２’−ビ（１，３，２−ジオキサボロラニル）１４０ｍｇ（０．５５ｍｍｏｌ）、トリメチル（２，２，２−トリフルオロエトキシ）シラン１８０ｍｇ（１．０５ｍｍｏｌ）およびテトラヒドロフラン０．５ｍＬを加えて密閉し、１００℃で１２時間攪拌した。反応容器を室温まで冷却した後、飽和塩化アンモニウム水溶液１ｍＬを加え酢酸エチル８ｍＬで３回抽出し、得られた有機相を合わせた。溶媒を減圧留去し、残渣をシリカゲルカラムクロマトグラフィ（ヘキサン：クロロホルム：酢酸エチル＝１６：４：０〜１６：４：１）を用いて精製することにより、フェニル［４−（４，４，５，５−テトラメチル−１，３，２−ジオキサボロラン−２−イル）フェニル］ケトン１１２ｍｇ（白色固体、収率７３％）を得た。
^１Ｈ−ＮＭＲ（ＣＤＣｌ_３，４００ＭＨｚ）δ７．９２（ｄ，Ｊ＝８．２Ｈｚ，２Ｈ），７．８１−７．７６（ｍ，４Ｈ），７．５９（ｄｄ，Ｊ＝７．４Ｈｚ，７．４Ｈｚ，１Ｈ），７．４８（ｄｄ，Ｊ＝７．４Ｈｚ，７．４Ｈｚ，２Ｈ），１．３７（ｓ，１２Ｈ）。

Under argon atmosphere, dichlorobis (trimethylphosphine) nickel 1.4 mg (0.005 mmol), (4-chlorophenyl) phenylketone 108 mg (0.5 mmol), cesium fluoride 152 mg (1.0 mmol), 4,4, 5,5,4 ′, 4 ′, 5 ′, 5′-octamethyl-2,2′-bi (1,3,2-dioxaborolanyl) 140 mg (0.55 mmol), trimethyl (2,2, 180 mg (1.05 mmol) of 2-trifluoroethoxy) silane and 0.5 mL of tetrahydrofuran were added and sealed, followed by stirring at 100 ° C. for 12 hours. After the reaction vessel was cooled to room temperature, 1 mL of a saturated aqueous ammonium chloride solution was added, followed by extraction three times with 8 mL of ethyl acetate, and the resulting organic phases were combined. The solvent was distilled off under reduced pressure, and the residue was purified by silica gel column chromatography (hexane: chloroform: ethyl acetate = 16: 4: 0 to 16: 4: 1), whereby phenyl [4- (4,4,5 , 5-Tetramethyl-1,3,2-dioxaborolan-2-yl) phenyl] ketone 112 mg (white solid, 73% yield).
¹ H-NMR (CDCl ₃ , 400 MHz) δ 7.92 (d, J = 8.2 Hz, 2H), 7.81-7.76 (m, 4H), 7.59 (dd, J = 7.4 Hz, 7.4 Hz, 1H), 7.48 (dd, J = 7.4 Hz, 7.4 Hz, 2H), 1.37 (s, 12H).

  Example-23

アルゴン雰囲気下、反応容器にジクロロビス（トリメチルホスフィン）ニッケル４．２ｍｇ（０．０１５ｍｍｏｌ）、（２−クロロフェニル）シクロペンチルケトン１０１ｍｇ（０．５ｍｍｏｌ）、フッ化セシウム１５２ｍｇ（１．０ｍｍｏｌ）、４，４，５，５，４’，４’，５’，５’−オクタメチル−２，２’−ビ（１，３，２−ジオキサボロラニル）１４０ｍｇ（０．５５ｍｍｏｌ）、トリメチル（２，２，２−トリフルオロエトキシ）シラン１８０ｍｇ（１．０５ｍｍｏｌ）およびテトラヒドロフラン０．５ｍＬを加えて密閉し、１００℃で１２時間攪拌した。反応容器を室温まで冷却した後、飽和塩化アンモニウム水溶液１ｍＬを加え酢酸エチル８ｍＬで３回抽出し、得られた有機相を合わせた。溶媒を減圧留去し、残渣をシリカゲルカラムクロマトグラフィ（ヘキサン：クロロホルム：酢酸エチル＝１６：４：０〜１６：４：１）を用いて精製することにより、シクロペンチル［２−（４，４，５，５−テトラメチル−１，３，２−ジオキサボロラン−２−イル）］フェニルケトン１０７ｍｇ（無色液体、収率７３％）を得た。
^１Ｈ−ＮＭＲ（ＣＤＣｌ_３，４００ＭＨｚ）δ７．７８（ｄ，Ｊ＝７．２Ｈｚ，１Ｈ），７．５２（ｄｄｄ，Ｊ＝０．８Ｈｚ，１．７Ｈｚ，７．２Ｈｚ，１Ｈ），７．４９（ｄｄｄ，Ｊ＝０．８Ｈｚ，７．２Ｈｚ，７．２Ｈｚ，１Ｈ），７．３９（ｄｄｄ，Ｊ＝１．７Ｈｚ，７．２Ｈｚ，７．２Ｈｚ，１Ｈ），３．６５（ｄｄｄ，Ｊ＝７．２Ｈｚ，８．４Ｈｚ，１５．７Ｈｚ，１Ｈ），２．００−１．８６（ｍ，４Ｈ），１．７７−１．５７（ｍ，４Ｈ），１．４２（ｓ，１２Ｈ）。

Under an argon atmosphere, 4.2 mg (0.015 mmol) of dichlorobis (trimethylphosphine) nickel, 101 mg (0.5 mmol) of (2-chlorophenyl) cyclopentyl ketone, 152 mg (1.0 mmol) of cesium fluoride, 4, 4, 5,5,4 ′, 4 ′, 5 ′, 5′-octamethyl-2,2′-bi (1,3,2-dioxaborolanyl) 140 mg (0.55 mmol), trimethyl (2,2, 180 mg (1.05 mmol) of 2-trifluoroethoxy) silane and 0.5 mL of tetrahydrofuran were added and sealed, followed by stirring at 100 ° C. for 12 hours. After the reaction vessel was cooled to room temperature, 1 mL of a saturated aqueous ammonium chloride solution was added, followed by extraction three times with 8 mL of ethyl acetate, and the resulting organic phases were combined. The solvent was distilled off under reduced pressure, and the residue was purified by silica gel column chromatography (hexane: chloroform: ethyl acetate = 16: 4: 0 to 16: 4: 1), whereby cyclopentyl [2- (4,4,5 , 5-tetramethyl-1,3,2-dioxaborolan-2-yl)] phenylketone (107 mg, colorless liquid, yield 73%) was obtained.
¹ H-NMR (CDCl ₃ , 400 MHz) δ 7.78 (d, J = 7.2 Hz, 1H), 7.52 (ddd, J = 0.8 Hz, 1.7 Hz, 7.2 Hz, 1H), 7. 49 (ddd, J = 0.8 Hz, 7.2 Hz, 7.2 Hz, 1H), 7.39 (ddd, J = 1.7 Hz, 7.2 Hz, 7.2 Hz, 1H), 3.65 (ddd, J = 7.2 Hz, 8.4 Hz, 15.7 Hz, 1H), 2.00-1.86 (m, 4H), 1.77-1.57 (m, 4H), 1.42 (s, 12H) ).

  Example-24

アルゴン雰囲気下、反応容器にジクロロビス（トリメチルホスフィン）ニッケル１．４ｍｇ（０．００５ｍｍｏｌ）、４−クロロベンズアミド７７．４ｍｇ（０．５ｍｍｏｌ）、フッ化セシウム１５２ｍｇ（１．０ｍｍｏｌ）、４，４，５，５，４’，４’，５’，５’−オクタメチル−２，２’−ビ（１，３，２−ジオキサボロラニル）１４０ｍｇ（０．５５ｍｍｏｌ）、トリメチル（２，２，２−トリフルオロエトキシ）シラン１８０ｍｇ（１．０５ｍｍｏｌ）および１，４−ジオキサン０．５ｍＬを加えて密閉し、１００℃で１２時間攪拌した。反応容器を室温まで冷却した後、飽和塩化アンモニウム水溶液１ｍＬを加え酢酸エチル８ｍＬで３回抽出し、得られた有機相を合わせた。溶媒を減圧留去し、残渣をシリカゲルカラムクロマトグラフィ（ヘキサン：クロロホルム：酢酸エチル＝４：１：０〜４：１：１）を用いて精製することにより、４−（４，４，５，５−テトラメチル−１，３，２−ジオキサボロラン−２−イル）ベンズアミド９２ｍｇ（白色固体、収率７５％）を得た。
^１Ｈ−ＮＭＲ（ＣＤＣｌ_３，４００ＭＨｚ）δ７．８８（ｄ，Ｊ＝８．２Ｈｚ，２Ｈ），７．８０（ｄ，Ｊ＝８．２Ｈｚ，２Ｈ），６．２１（ｓ，２Ｈ），１．３６（ｓ，１２Ｈ）。

Under argon atmosphere, dichlorobis (trimethylphosphine) nickel 1.4 mg (0.005 mmol), 4-chlorobenzamide 77.4 mg (0.5 mmol), cesium fluoride 152 mg (1.0 mmol), 4, 4, 5 , 5,4 ′, 4 ′, 5 ′, 5′-octamethyl-2,2′-bi (1,3,2-dioxaborolanyl) 140 mg (0.55 mmol), trimethyl (2,2,2) -Trifluoroethoxy) silane 180 mg (1.05 mmol) and 1,4-dioxane 0.5 mL were added and sealed, and the mixture was stirred at 100 ° C. for 12 hours. After the reaction vessel was cooled to room temperature, 1 mL of a saturated aqueous ammonium chloride solution was added, followed by extraction three times with 8 mL of ethyl acetate, and the resulting organic phases were combined. The solvent was distilled off under reduced pressure, and the residue was purified by silica gel column chromatography (hexane: chloroform: ethyl acetate = 4: 1: 0 to 4: 1: 1) to give 4- (4, 4, 5, 5 -92 mg (white solid, yield 75%) of tetramethyl-1,3,2-dioxaborolan-2-yl) benzamide was obtained.
¹ H-NMR (CDCl ₃ , 400 MHz) δ 7.88 (d, J = 8.2 Hz, 2H), 7.80 (d, J = 8.2 Hz, 2H), 6.21 (s, 2H), 1 .36 (s, 12H).

  Example-25

アルゴン雰囲気下、反応容器にジクロロビス（トリメチルホスフィン）ニッケル４．２ｍｇ（０．０１５ｍｍｏｌ）、４−ブチル−１−クロロベンゼン８３．５ｍｇ（０．５ｍｍｏｌ）、フッ化セシウム１５２ｍｇ（１．０ｍｍｏｌ）、４，４，５，５，４’，４’，５’，５’−オクタメチル−２，２’−ビ（１，３，２−ジオキサボロラニル）１４０ｍｇ（０．５５ｍｍｏｌ）、トリメチル（２，２，２−トリフルオロエトキシ）シラン１８０ｍｇ（１．０５ｍｍｏｌ）およびテトラヒドロフラン０．５ｍＬを加えて密閉し、１００℃で１２時間攪拌した。反応容器を室温まで冷却した後、飽和塩化アンモニウム水溶液１ｍＬを加え酢酸エチル８ｍＬで３回抽出し、得られた有機相を合わせた。溶媒を減圧留去し、残渣をシリカゲルカラムクロマトグラフィ（ヘキサン：クロロホルム：酢酸エチル＝１６：４：０〜１６：４：１）を用いて精製することにより、２−（４−ブチルフェニル）−４，４，５，５−テトラメチル−１，３，２−ジオキサボロラン９３ｍｇ（白色固体、収率７２％）を得た。
^１Ｈ−ＮＭＲ（ＣＤＣｌ_３，４００ＭＨｚ）δ７．７２（ｄ，Ｊ＝８．０Ｈｚ，２Ｈ），７．１９（ｄ，Ｊ＝８．０Ｈｚ，２Ｈ），２．６２（ｔ，Ｊ＝７．６Ｈｚ，２Ｈ），１．６２−１．５７（ｍ，２Ｈ），１．３９−１．２８（ｍ，２Ｈ），１．３３（ｓ，１２Ｈ），０．９１（ｔ，Ｊ＝７．３Ｈｚ，３Ｈ）。

Under an argon atmosphere, 4.2 mg (0.015 mmol) of dichlorobis (trimethylphosphine) nickel, 83.5 mg (0.5 mmol) of 4-butyl-1-chlorobenzene, 152 mg (1.0 mmol) of cesium fluoride, 4, 4,5,5,4 ′, 4 ′, 5 ′, 5′-octamethyl-2,2′-bi (1,3,2-dioxaborolanyl) 140 mg (0.55 mmol), trimethyl (2, 180 mg (1.05 mmol) of 2,2-trifluoroethoxy) silane and 0.5 mL of tetrahydrofuran were added and sealed, followed by stirring at 100 ° C. for 12 hours. After the reaction vessel was cooled to room temperature, 1 mL of a saturated aqueous ammonium chloride solution was added, followed by extraction three times with 8 mL of ethyl acetate, and the resulting organic phases were combined. The solvent was distilled off under reduced pressure, and the residue was purified by silica gel column chromatography (hexane: chloroform: ethyl acetate = 16: 4: 0 to 16: 4: 1) to give 2- (4-butylphenyl) -4 , 4,5,5-tetramethyl-1,3,2-dioxaborolane (93 mg, white solid, yield 72%) was obtained.
¹ H-NMR (CDCl ₃ , 400 MHz) δ 7.72 (d, J = 8.0 Hz, 2H), 7.19 (d, J = 8.0 Hz, 2H), 2.62 (t, J = 7. 6 Hz, 2H), 1.62-1.57 (m, 2H), 1.39-1.28 (m, 2H), 1.33 (s, 12H), 0.91 (t, J = 7. 3Hz, 3H).

  Example-26

アルゴン雰囲気下、反応容器にジクロロビス（トリメチルホスフィン）ニッケル４．２ｍｇ（０．０１５ｍｍｏｌ）、４−ｔｅｒｔ−ブチル−１−クロロベンゼン８３．８ｍｇ（０．５ｍｍｏｌ）、フッ化セシウム１５２ｍｇ（１．０ｍｍｏｌ）、４，４，５，５，４’，４’，５’，５’−オクタメチル−２，２’−ビ（１，３，２−ジオキサボロラニル）１４０ｍｇ（０．５５ｍｍｏｌ）、トリメチル（２，２，２−トリフルオロエトキシ）シラン１８０ｍｇ（１．０５ｍｍｏｌ）およびテトラヒドロフラン０．５ｍＬを加えて密閉し、１００℃で１２時間攪拌した。反応容器を室温まで冷却した後、飽和塩化アンモニウム水溶液１ｍＬを加え酢酸エチル８ｍＬで３回抽出し、得られた有機相を合わせた。溶媒を減圧留去し、残渣をシリカゲルカラムクロマトグラフィ（ヘキサン：クロロホルム：酢酸エチル＝１６：４：０〜１６：４：１）を用いて精製することにより、２−（４−ｔｅｒｔ−ブチルフェニル）−４，４，５，５−テトラメチル−１，３，２−ジオキサボロラン９３ｍｇ（白色固体、収率７２％）を得た。
^１Ｈ−ＮＭＲ（ＣＤＣｌ_３，４００ＭＨｚ）δ７．７６（ｄ，Ｊ＝８．２Ｈｚ，２Ｈ），７．４０（ｄ，Ｊ＝８．２Ｈｚ，２Ｈ），１．３３（ｓ，１２Ｈ），１．３２（ｓ，９Ｈ）。

Under an argon atmosphere, 4.2 mg (0.015 mmol) of dichlorobis (trimethylphosphine) nickel, 83.8 mg (0.5 mmol) of 4-tert-butyl-1-chlorobenzene, 152 mg (1.0 mmol) of cesium fluoride, 4,4,5,5,4 ′, 4 ′, 5 ′, 5′-octamethyl-2,2′-bi (1,3,2-dioxaborolanyl) 140 mg (0.55 mmol), trimethyl ( 180 mg (1.05 mmol) of 2,2,2-trifluoroethoxy) silane and 0.5 mL of tetrahydrofuran were added and sealed, and the mixture was stirred at 100 ° C. for 12 hours. After the reaction vessel was cooled to room temperature, 1 mL of a saturated aqueous ammonium chloride solution was added, followed by extraction three times with 8 mL of ethyl acetate, and the resulting organic phases were combined. The solvent was distilled off under reduced pressure, and the residue was purified using silica gel column chromatography (hexane: chloroform: ethyl acetate = 16: 4: 0 to 16: 4: 1) to give 2- (4-tert-butylphenyl). 93 mg (white solid, yield 72%) of -4,4,5,5-tetramethyl-1,3,2-dioxaborolane was obtained.
¹ H-NMR (CDCl ₃ , 400 MHz) δ 7.76 (d, J = 8.2 Hz, 2H), 7.40 (d, J = 8.2 Hz, 2H), 1.33 (s, 12H), 1 .32 (s, 9H).

  Example-27

アルゴン雰囲気下、反応容器にジクロロビス（トリメチルホスフィン）ニッケル２．８ｍｇ（０．０１ｍｍｏｌ）、２−クロロベンゾトリフルオリド８９．６ｍｇ（０．５ｍｍｏｌ）、フッ化セシウム１５２ｍｇ（１．０ｍｍｏｌ）、４，４，５，５，４’，４’，５’，５’−オクタメチル−２，２’−ビ（１，３，２−ジオキサボロラニル）１４０ｍｇ（０．５５ｍｍｏｌ）、トリメチル（２，２，２−トリフルオロエトキシ）シラン１８０ｍｇ（１．０５ｍｍｏｌ）およびテトラヒドロフラン０．５ｍＬを加えて密閉し、１００℃で１２時間攪拌した。反応容器を室温まで冷却した後、飽和塩化アンモニウム水溶液１ｍＬを加え酢酸エチル８ｍＬで３回抽出し、得られた有機相を合わせた。溶媒を減圧留去し、残渣をシリカゲルカラムクロマトグラフィ（ヘキサン：クロロホルム：酢酸エチル＝１６：４：０〜１６：４：１）を用いて精製することにより、４，４，５，５−テトラメチル−２−［２−（トリフルオロメチル）フェニル］−１，３，２−ジオキサボロラン１１９ｍｇ（無色液体、収率８８％）を得た。
^１Ｈ−ＮＭＲ（ＣＤＣｌ_３，４００ＭＨｚ）δ７．７３−７．６４（ｍ，２Ｈ），７．５３−７．４７（ｍ，２Ｈ），１．３７（ｓ，１２Ｈ）．
^１９Ｆ−ＮＭＲ（ＣＤＣｌ_３，３７６ＭＨｚ）δ−５９．７（ｓ，３Ｆ）。

Under an argon atmosphere, 2.8 mg (0.01 mmol) of dichlorobis (trimethylphosphine) nickel, 89.6 mg (0.5 mmol) of 2-chlorobenzotrifluoride, 152 mg (1.0 mmol) of cesium fluoride, 4,4 , 5,5,4 ′, 4 ′, 5 ′, 5′-octamethyl-2,2′-bi (1,3,2-dioxaborolanyl) 140 mg (0.55 mmol), trimethyl (2,2 , 2-trifluoroethoxy) silane (180 mg, 1.05 mmol) and tetrahydrofuran (0.5 mL) were added, and the mixture was sealed and stirred at 100 ° C. for 12 hr. After the reaction vessel was cooled to room temperature, 1 mL of a saturated aqueous ammonium chloride solution was added, followed by extraction three times with 8 mL of ethyl acetate, and the resulting organic phases were combined. The solvent was distilled off under reduced pressure, and the residue was purified by silica gel column chromatography (hexane: chloroform: ethyl acetate = 16: 4: 0 to 16: 4: 1) to give 4,4,5,5-tetramethyl. 119 mg (colorless liquid, 88% yield) of 2- [2- (trifluoromethyl) phenyl] -1,3,2-dioxaborolane was obtained.
_{^{1 H-NMR (CDCl 3,}} 400MHz) δ7.73-7.64 (m, 2H), 7.53-7.47 (m, 2H), 1.37 (s, 12H).
¹⁹ F-NMR (CDCl ₃ , 376 MHz) δ-59.7 (s, 3F).

  Example-28

アルゴン雰囲気下、反応容器にジクロロビス（トリメチルホスフィン）ニッケル４．２ｍｇ（０．０１５ｍｍｏｌ）、１−クロロ−４−（ジエトキシメチル）ベンゼン１０８．６ｍｇ（０．５ｍｍｏｌ）、フッ化セシウム１５２ｍｇ（１．０ｍｍｏｌ）、４，４，５，５，４’，４’，５’，５’−オクタメチル−２，２’−ビ（１，３，２−ジオキサボロラニル）１４０ｍｇ（０．５５ｍｍｏｌ）、トリメチル（２，２，２−トリフルオロエトキシ）シラン１８０ｍｇ（１．０５ｍｍｏｌ）およびテトラヒドロフラン０．５ｍＬを加えて密閉し、１００℃で１２時間攪拌した。反応容器を室温まで冷却した後、飽和塩化アンモニウム水溶液１ｍＬを加え酢酸エチル８ｍＬで３回抽出し、得られた有機相を合わせた。溶媒を減圧留去し、残渣をシリカゲルカラムクロマトグラフィ（ヘキサン：クロロホルム：酢酸エチル＝１６：４：０〜１６：４：１）を用いて精製することにより、２−［４−（ジエトキシメチル）フェニル］−４，４，５，５−テトラメチル−１，３，２−ジオキサボロラン１２７ｍｇ（無色液体、収率８２％）を得た。
^１Ｈ−ＮＭＲ（ＣＤＣｌ_３，４００ＭＨｚ）δ７．８１（ｄ，Ｊ＝８．０Ｈｚ，２Ｈ），７．４８（ｄ，Ｊ＝８．０Ｈｚ，２Ｈ），５．５２（ｓ，１Ｈ），３．６３−３．４９（ｍ，４Ｈ），１．３４（ｓ，１２Ｈ），１．２３（ｔ，Ｊ＝７．０Ｈｚ，６Ｈ）。

Under an argon atmosphere, 4.2 mg (0.015 mmol) of dichlorobis (trimethylphosphine) nickel, 108.6 mg (0.5 mmol) of 1-chloro-4- (diethoxymethyl) benzene, 152 mg of cesium fluoride (1. 0 mmol), 4,4,5,5,4 ′, 4 ′, 5 ′, 5′-octamethyl-2,2′-bi (1,3,2-dioxaborolanyl) 140 mg (0.55 mmol) , 180 mg (1.05 mmol) of trimethyl (2,2,2-trifluoroethoxy) silane and 0.5 mL of tetrahydrofuran were added and sealed, followed by stirring at 100 ° C. for 12 hours. After the reaction vessel was cooled to room temperature, 1 mL of a saturated aqueous ammonium chloride solution was added, followed by extraction three times with 8 mL of ethyl acetate, and the resulting organic phases were combined. The solvent was distilled off under reduced pressure, and the residue was purified using silica gel column chromatography (hexane: chloroform: ethyl acetate = 16: 4: 0 to 16: 4: 1) to give 2- [4- (diethoxymethyl) Phenyl] -4,4,5,5-tetramethyl-1,3,2-dioxaborolane (127 mg, colorless liquid, yield 82%) was obtained.
¹ H-NMR (CDCl ₃ , 400 MHz) δ 7.81 (d, J = 8.0 Hz, 2H), 7.48 (d, J = 8.0 Hz, 2H), 5.52 (s, 1H), 3 .63-3.49 (m, 4H), 1.34 (s, 12H), 1.23 (t, J = 7.0 Hz, 6H).

  Example-29

アルゴン雰囲気下、反応容器にジクロロビス（トリメチルホスフィン）ニッケル２．８ｍｇ（０．０１ｍｍｏｌ）、５−クロロ−２−フルオロトルエン７２．４ｍｇ（０．５ｍｍｏｌ）、フッ化セシウム１５２ｍｇ（１．０ｍｍｏｌ）、４，４，５，５，４’，４’，５’，５’−オクタメチル−２，２’−ビ（１，３，２−ジオキサボロラニル）１４０ｍｇ（０．５５ｍｍｏｌ）、トリメチル（２，２，２−トリフルオロエトキシ）シラン１８０ｍｇ（１．０５ｍｍｏｌ）およびテトラヒドロフラン０．５ｍＬを加えて密閉し、１００℃で１２時間攪拌した。反応容器を室温まで冷却した後、飽和塩化アンモニウム水溶液１ｍＬを加え酢酸エチル８ｍＬで３回抽出し、得られた有機相を合わせた。溶媒を減圧留去し、残渣をシリカゲルカラムクロマトグラフィ（ヘキサン：クロロホルム：酢酸エチル＝１６：４：０〜１６：４：１）を用いて精製することにより、２−（４−フルオロ−３−メチルフェニル）−４，４，５，５−テトラメチル−１，３，２−ジオキサボロラン１０４ｍｇ（無色液体、収率８８％）を得た。
^１Ｈ−ＮＭＲ（ＣＤＣｌ_３，４００ＭＨｚ）δ７．６６−７．５９（ｍ，２Ｈ），６．９９（ｄｄ，Ｊ＝８．１Ｈｚ，１０．０Ｈｚ，１Ｈ），２．２７（ｄ，Ｊ＝１．８Ｈｚ，３Ｈ），１．３３（ｓ，１２Ｈ）．
^１９Ｆ−ＮＭＲ（ＣＤＣｌ_３，３７６ＭＨｚ）δ−１１２．９（ｓ，１Ｆ）。

Under an argon atmosphere, 2.8 mg (0.01 mmol) of dichlorobis (trimethylphosphine) nickel, 72.4 mg (0.5 mmol) of 5-chloro-2-fluorotoluene, 152 mg (1.0 mmol) of cesium fluoride, 4 , 4,5,5,4 ′, 4 ′, 5 ′, 5′-octamethyl-2,2′-bi (1,3,2-dioxaborolanyl) 140 mg (0.55 mmol), trimethyl (2 , 2,2-trifluoroethoxy) silane 180 mg (1.05 mmol) and tetrahydrofuran 0.5 mL were added and sealed, and the mixture was stirred at 100 ° C. for 12 hours. After the reaction vessel was cooled to room temperature, 1 mL of a saturated aqueous ammonium chloride solution was added, followed by extraction three times with 8 mL of ethyl acetate, and the resulting organic phases were combined. The solvent was distilled off under reduced pressure, and the residue was purified using silica gel column chromatography (hexane: chloroform: ethyl acetate = 16: 4: 0 to 16: 4: 1) to give 2- (4-fluoro-3-methyl). Phenyl) -4,4,5,5-tetramethyl-1,3,2-dioxaborolane (104 mg, colorless liquid, yield 88%) was obtained.
¹ H-NMR (CDCl ₃ , 400 MHz) δ 7.66-7.59 (m, 2H), 6.99 (dd, J = 8.1 Hz, 10.0 Hz, 1H), 2.27 (d, J = 1.8 Hz, 3H), 1.33 (s, 12H).
¹⁹ F-NMR (CDCl ₃ , 376 MHz) δ-112.9 (s, 1F).

  Example-30

アルゴン雰囲気下、反応容器にジクロロビス（トリメチルホスフィン）ニッケル４．２ｍｇ（０．０１５ｍｍｏｌ）、１−クロロ−４−イソプロペニルベンゼン７４．７ｍｇ（０．５ｍｍｏｌ）、フッ化セシウム１５２ｍｇ（１．０ｍｍｏｌ）、４，４，５，５，４’，４’，５’，５’−オクタメチル−２，２’−ビ（１，３，２−ジオキサボロラニル）１４０ｍｇ（０．５５ｍｍｏｌ）、トリメチル（２，２，２−トリフルオロエトキシ）シラン１８０ｍｇ（１．０５ｍｍｏｌ）およびテトラヒドロフラン０．５ｍＬを加えて密閉し、１００℃で１２時間攪拌した。反応容器を室温まで冷却した後、飽和塩化アンモニウム水溶液１ｍＬを加え酢酸エチル８ｍＬで３回抽出し、得られた有機相を合わせた。溶媒を減圧留去し、残渣をシリカゲルカラムクロマトグラフィ（ヘキサン：クロロホルム：酢酸エチル＝１６：４：０〜１６：４：１）を用いて精製することにより、４，４，５，５−テトラメチル−２−（４−イソプロペニルフェニル）−１，３，２−ジオキサボロラン９４ｍｇ（無色液体、収率７９％）を得た。
^１Ｈ−ＮＭＲ（ＣＤＣｌ_３，４００ＭＨｚ）δ７．７７（ｄ，Ｊ＝８．３Ｈｚ，２Ｈ），７．４６（ｄ，Ｊ＝８．３Ｈｚ，２Ｈ），５．４１（ｄｄ，Ｊ＝０．８Ｈｚ，１．５Ｈｚ，１Ｈ），５．１１（ｄｄ，Ｊ＝１．５Ｈｚ，１．５Ｈｚ，１Ｈ），２．１５（ｄｄ，Ｊ＝０．８Ｈｚ，１．５Ｈｚ，３Ｈ），１．３３（ｓ，１２Ｈ）。

Under an argon atmosphere, 4.2 mg (0.015 mmol) of dichlorobis (trimethylphosphine) nickel, 74.7 mg (0.5 mmol) of 1-chloro-4-isopropenylbenzene, 152 mg (1.0 mmol) of cesium fluoride, 4,4,5,5,4 ′, 4 ′, 5 ′, 5′-octamethyl-2,2′-bi (1,3,2-dioxaborolanyl) 140 mg (0.55 mmol), trimethyl ( 180 mg (1.05 mmol) of 2,2,2-trifluoroethoxy) silane and 0.5 mL of tetrahydrofuran were added and sealed, and the mixture was stirred at 100 ° C. for 12 hours. After the reaction vessel was cooled to room temperature, 1 mL of a saturated aqueous ammonium chloride solution was added, followed by extraction three times with 8 mL of ethyl acetate, and the resulting organic phases were combined. The solvent was distilled off under reduced pressure, and the residue was purified by silica gel column chromatography (hexane: chloroform: ethyl acetate = 16: 4: 0 to 16: 4: 1) to give 4,4,5,5-tetramethyl. 94 mg (colorless liquid, yield 79%) of -2- (4-isopropenylphenyl) -1,3,2-dioxaborolane was obtained.
¹ H-NMR (CDCl ₃ , 400 MHz) δ 7.77 (d, J = 8.3 Hz, 2H), 7.46 (d, J = 8.3 Hz, 2H), 5.41 (dd, J = 0. 8Hz, 1.5Hz, 1H), 5.11 (dd, J = 1.5Hz, 1.5Hz, 1H), 2.15 (dd, J = 0.8Hz, 1.5Hz, 3H), 1.33 (S, 12H).

  Example-31

アルゴン雰囲気下、反応容器にジクロロビス（トリメチルホスフィン）ニッケル４．２ｍｇ（０．０１５ｍｍｏｌ）、５−クロロ−２−フルオロアニリン７２．８ｍｇ（０．５ｍｍｏｌ）、フッ化セシウム１５２ｍｇ（１．０ｍｍｏｌ）、４，４，５，５，４’，４’，５’，５’−オクタメチル−２，２’−ビ（１，３，２−ジオキサボロラニル）１４０ｍｇ（０．５５ｍｍｏｌ）、トリメチル（２，２，２−トリフルオロエトキシ）シラン１８０ｍｇ（１．０５ｍｍｏｌ）およびテトラヒドロフラン０．５ｍＬを加えて密閉し、１００℃で１２時間攪拌した。反応容器を室温まで冷却した後、飽和塩化アンモニウム水溶液１ｍＬを加え酢酸エチル８ｍＬで３回抽出し、得られた有機相を合わせた。溶媒を減圧留去し、残渣をシリカゲルカラムクロマトグラフィ（ヘキサン：クロロホルム：酢酸エチル＝４：１：０〜４：１：１）を用いて精製することにより、２−フルオロ−５−（４，４，５，５−テトラメチル−１，３，２−ジオキサボロラン−２−イル）アニリン９６ｍｇ（淡黄色液体、収率８１％）を得た。
^１Ｈ−ＮＭＲ（ＣＤＣｌ_３，４００ＭＨｚ）δ７．２３（ｄｄ，Ｊ＝１．６Ｈｚ，９．６Ｈｚ，１Ｈ），７．１６（ｄｄｄ，Ｊ＝１．６Ｈｚ，５．３Ｈｚ，８．０Ｈｚ，１Ｈ），６．９７（ｄｄ，８．０Ｈｚ，１１．３Ｈｚ，１Ｈ），３．６８（ｓ，２Ｈ），１．３３（ｓ，１２Ｈ）．
^１９Ｆ−ＮＭＲ（ＣＤＣｌ_３，３７６ＭＨｚ）δ−１３０．９（ｓ，１Ｆ）。

Under argon atmosphere, dichlorobis (trimethylphosphine) nickel 4.2 mg (0.015 mmol), 5-chloro-2-fluoroaniline 72.8 mg (0.5 mmol), cesium fluoride 152 mg (1.0 mmol), 4 , 4,5,5,4 ′, 4 ′, 5 ′, 5′-octamethyl-2,2′-bi (1,3,2-dioxaborolanyl) 140 mg (0.55 mmol), trimethyl (2 , 2,2-trifluoroethoxy) silane 180 mg (1.05 mmol) and tetrahydrofuran 0.5 mL were added and sealed, and the mixture was stirred at 100 ° C. for 12 hours. After the reaction vessel was cooled to room temperature, 1 mL of a saturated aqueous ammonium chloride solution was added, followed by extraction three times with 8 mL of ethyl acetate, and the resulting organic phases were combined. The solvent was distilled off under reduced pressure, and the residue was purified by silica gel column chromatography (hexane: chloroform: ethyl acetate = 4: 1: 0 to 4: 1: 1) to give 2-fluoro-5- (4,4 , 5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) aniline (96 mg, pale yellow liquid, 81% yield) was obtained.
¹ H-NMR (CDCl ₃ , 400 MHz) δ 7.23 (dd, J = 1.6 Hz, 9.6 Hz, 1H), 7.16 (ddd, J = 1.6 Hz, 5.3 Hz, 8.0 Hz, 1H) ), 6.97 (dd, 8.0 Hz, 11.3 Hz, 1H), 3.68 (s, 2H), 1.33 (s, 12H).
¹⁹ F-NMR (CDCl ₃ , 376 MHz) δ-130.9 (s, 1F).

  Example-32

アルゴン雰囲気下、反応容器にジクロロビス（トリメチルホスフィン）ニッケル４．２ｍｇ（０．０１５ｍｍｏｌ）、４−（４−クロロフェニル）モルホリン９８．４ｍｇ（０．５ｍｍｏｌ）、フッ化セシウム１５２ｍｇ（１．０ｍｍｏｌ）、４，４，５，５，４’，４’，５’，５’−オクタメチル−２，２’−ビ（１，３，２−ジオキサボロラニル）１４０ｍｇ（０．５５ｍｍｏｌ）、トリメチル（２，２，２−トリフルオロエトキシ）シラン１８０ｍｇ（１．０５ｍｍｏｌ）およびテトラヒドロフラン０．５ｍＬを加えて密閉し、１００℃で１２時間攪拌した。反応容器を室温まで冷却した後、飽和塩化アンモニウム水溶液１ｍＬを加え酢酸エチル８ｍＬで３回抽出し、得られた有機相を合わせた。溶媒を減圧留去し、残渣をシリカゲルカラムクロマトグラフィ（ヘキサン：クロロホルム：酢酸エチル＝４：１：０〜４：１：１）を用いて精製することにより、４−［４−（４，４，５，５−テトラメチル−１，３，２−ジオキサボロラン−２−イル）フェニル］モルホリン１２３ｍｇ（白色固体、収率８６％）を得た。
^１Ｈ−ＮＭＲ（ＣＤＣｌ_３，４００ＭＨｚ）δ７．７２（ｄ，Ｊ＝８．６Ｈｚ，２Ｈ），６．８７（ｄ，Ｊ＝８．６Ｈｚ，２Ｈ），３．８４（ｔ，Ｊ＝４．８Ｈｚ，４Ｈ），３．２１（ｔ，Ｊ＝４．８Ｈｚ，４Ｈ），１．３２（ｓ，１２Ｈ）。

Under an argon atmosphere, dichlorobis (trimethylphosphine) nickel 4.2 mg (0.015 mmol), 4- (4-chlorophenyl) morpholine 98.4 mg (0.5 mmol), cesium fluoride 152 mg (1.0 mmol), 4 , 4,5,5,4 ′, 4 ′, 5 ′, 5′-octamethyl-2,2′-bi (1,3,2-dioxaborolanyl) 140 mg (0.55 mmol), trimethyl (2 , 2,2-trifluoroethoxy) silane 180 mg (1.05 mmol) and tetrahydrofuran 0.5 mL were added and sealed, and the mixture was stirred at 100 ° C. for 12 hours. After the reaction vessel was cooled to room temperature, 1 mL of a saturated aqueous ammonium chloride solution was added, followed by extraction three times with 8 mL of ethyl acetate, and the resulting organic phases were combined. The solvent was distilled off under reduced pressure, and the residue was purified using silica gel column chromatography (hexane: chloroform: ethyl acetate = 4: 1: 0 to 4: 1: 1) to give 4- [4- (4,4,4 123 mg (white solid, yield 86%) of 5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) phenyl] morpholine was obtained.
¹ H-NMR (CDCl ₃ , 400 MHz) δ 7.72 (d, J = 8.6 Hz, 2H), 6.87 (d, J = 8.6 Hz, 2H), 3.84 (t, J = 4. 8 Hz, 4H), 3.21 (t, J = 4.8 Hz, 4H), 1.32 (s, 12H).

  Example-33

アルゴン雰囲気下、反応容器にジクロロビス（トリメチルホスフィン）ニッケル１．４ｍｇ（０．００５ｍｍｏｌ）、Ｎ−（３−クロロフェニル）アセトアミド８５．１ｍｇ（０．５ｍｍｏｌ）、フッ化セシウム１５２ｍｇ（１．０ｍｍｏｌ）、４，４，５，５，４’，４’，５’，５’−オクタメチル−２，２’−ビ（１，３，２−ジオキサボロラニル）１４０ｍｇ（０．５５ｍｍｏｌ）、トリメチル（２，２，２−トリフルオロエトキシ）シラン１８０ｍｇ（１．０５ｍｍｏｌ）および１，４−ジオキサン０．５ｍＬを加えて密閉し、１００℃で１２時間攪拌した。反応容器を室温まで冷却した後、飽和塩化アンモニウム水溶液１ｍＬを加え酢酸エチル８ｍＬで３回抽出し、得られた有機相を合わせた。溶媒を減圧留去し、残渣をシリカゲルカラムクロマトグラフィ（ヘキサン：クロロホルム：酢酸エチル＝４：１：０〜４：１：１）を用いて精製することにより、Ｎ−［３−（４，４，５，５−テトラメチル−１，３，２−ジオキサボロラン−２−イル）フェニル］アセトアミド１２２ｍｇ（白色固体、収率９３％）を得た。
^１Ｈ−ＮＭＲ（ＣＤＣｌ_３，４００ＭＨｚ）δ７．８７（ｄ，Ｊ＝７．６Ｈｚ，１Ｈ），７．６６（ｓ，１Ｈ），７．５３（ｄ，Ｊ＝７．６Ｈｚ，１Ｈ），７．４９（ｓ，１Ｈ），７．３３（ｄｄ，Ｊ＝７．６Ｈｚ，７．６Ｈｚ，１Ｈ），２．１５（ｓ，３Ｈ），１．３２（ｓ，１２Ｈ）。

Under argon atmosphere, dichlorobis (trimethylphosphine) nickel 1.4 mg (0.005 mmol), N- (3-chlorophenyl) acetamide 85.1 mg (0.5 mmol), cesium fluoride 152 mg (1.0 mmol), 4 , 4,5,5,4 ′, 4 ′, 5 ′, 5′-octamethyl-2,2′-bi (1,3,2-dioxaborolanyl) 140 mg (0.55 mmol), trimethyl (2 , 2,2-trifluoroethoxy) silane (180 mg, 1.05 mmol) and 1,4-dioxane (0.5 mL) were added and sealed, and the mixture was stirred at 100 ° C. for 12 hours. After the reaction vessel was cooled to room temperature, 1 mL of a saturated aqueous ammonium chloride solution was added, followed by extraction three times with 8 mL of ethyl acetate, and the resulting organic phases were combined. The solvent was distilled off under reduced pressure, and the residue was purified by silica gel column chromatography (hexane: chloroform: ethyl acetate = 4: 1: 0 to 4: 1: 1) to give N- [3- (4,4,4 There was obtained 122 mg (white solid, yield 93%) of 5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) phenyl] acetamide.
¹ H-NMR (CDCl ₃ , 400 MHz) δ 7.87 (d, J = 7.6 Hz, 1H), 7.66 (s, 1H), 7.53 (d, J = 7.6 Hz, 1H), 7 .49 (s, 1H), 7.33 (dd, J = 7.6 Hz, 7.6 Hz, 1H), 2.15 (s, 3H), 1.32 (s, 12H).

  Example-34

アルゴン雰囲気下、反応容器にジクロロビス（トリメチルホスフィン）ニッケル４．２ｍｇ（０．０１５ｍｍｏｌ）、Ｎ−（２−クロロフェニル）ピバルアミド１０６ｍｇ（０．５ｍｍｏｌ）、フッ化セシウム１５２ｍｇ（１．０ｍｍｏｌ）、４，４，５，５，４’，４’，５’，５’−オクタメチル−２，２’−ビ（１，３，２−ジオキサボロラニル）１４０ｍｇ（０．５５ｍｍｏｌ）、トリメチル（２，２，２−トリフルオロエトキシ）シラン１８０ｍｇ（１．０５ｍｍｏｌ）および１，４−ジオキサン０．５ｍＬを加えて密閉し、１００℃で１２時間攪拌した。反応容器を室温まで冷却した後、飽和塩化アンモニウム水溶液１ｍＬを加え酢酸エチル８ｍＬで３回抽出し、得られた有機相を合わせた。溶媒を減圧留去し、残渣をシリカゲルカラムクロマトグラフィ（ヘキサン：クロロホルム：酢酸エチル＝４：１：０〜４：１：１）を用いて精製することにより、Ｎ−［２−（４，４，５，５−テトラメチル−１，３，２−ジオキサボロラン−２−イル）フェニル］ピバルアミド１２９ｍｇ（白色固体、収率８５％）を得た。
^１Ｈ−ＮＭＲ（ＣＤＣｌ_３，４００ＭＨｚ）δ９．５３（ｓ，１Ｈ），８．５６（ｄ，Ｊ＝７．４Ｈｚ，１Ｈ），７．７７（ｄ，Ｊ＝７．４Ｈｚ，１Ｈ），７．４５（ｄｄ，Ｊ＝７．４Ｈｚ，７．４Ｈｚ，１Ｈ），７．０５（ｄｄ，Ｊ＝７．４Ｈｚ，７．４Ｈｚ，１Ｈ），１．３８（ｓ，１２Ｈ），１．３３（ｓ，９Ｈ）。

Under an argon atmosphere, 4.2 mg (0.015 mmol) of dichlorobis (trimethylphosphine) nickel, 106 mg (0.5 mmol) of N- (2-chlorophenyl) pivalamide, 152 mg (1.0 mmol) of cesium fluoride, 4,4 , 5,5,4 ′, 4 ′, 5 ′, 5′-octamethyl-2,2′-bi (1,3,2-dioxaborolanyl) 140 mg (0.55 mmol), trimethyl (2,2 , 2-trifluoroethoxy) silane (180 mg, 1.05 mmol) and 1,4-dioxane (0.5 mL) were added and sealed, and the mixture was stirred at 100 ° C. for 12 hours. After the reaction vessel was cooled to room temperature, 1 mL of a saturated aqueous ammonium chloride solution was added, followed by extraction three times with 8 mL of ethyl acetate, and the resulting organic phases were combined. The solvent was distilled off under reduced pressure, and the residue was purified by silica gel column chromatography (hexane: chloroform: ethyl acetate = 4: 1: 0 to 4: 1: 1), whereby N- [2- (4,4,4 There was obtained 129 mg (white solid, yield 85%) of 5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) phenyl] pivalamide.
¹ H-NMR (CDCl ₃ , 400 MHz) δ9.53 (s, 1H), 8.56 (d, J = 7.4 Hz, 1H), 7.77 (d, J = 7.4 Hz, 1H), 7 .45 (dd, J = 7.4 Hz, 7.4 Hz, 1H), 7.05 (dd, J = 7.4 Hz, 7.4 Hz, 1H), 1.38 (s, 12H), 1.33 ( s, 9H).

  Example-35

アルゴン雰囲気下、反応容器にジクロロビス（トリメチルホスフィン）ニッケル４．２ｍｇ（０．０１５ｍｍｏｌ）、２−（４−クロロフェニル）−２，３−ジヒドロ−１Ｈ−ナフト［１，８−デ］−１，３，２−ジアゾボリニン１３９ｍｇ（０．５ｍｍｏｌ）、フッ化セシウム１５２ｍｇ（１．０ｍｍｏｌ）、４，４，５，５，４’，４’，５’，５’−オクタメチル−２，２’−ビ（１，３，２−ジオキサボロラニル）１４０ｍｇ（０．５５ｍｍｏｌ）、トリメチル（２，２，２−トリフルオロエトキシ）シラン１８０ｍｇ（１．０５ｍｍｏｌ）およびテトラヒドロフラン０．５ｍＬを加えて密閉し、１００℃で１２時間攪拌した。反応容器を室温まで冷却した後、飽和塩化アンモニウム水溶液１ｍＬを加え酢酸エチル８ｍＬで３回抽出し、得られた有機相を合わせた。溶媒を減圧留去し、残渣をシリカゲルカラムクロマトグラフィ（ヘキサン：クロロホルム：酢酸エチル＝４：１：０〜４：１：１）を用いて精製することにより、２−［４−（４，４，５，５−テトラメチル−１，３，２−ジオキサボロラン−２−イル）フェニル］−２，３−ジヒドロ−１Ｈ−ナフト［１，８−デ］−１，３，２−ジアゾボリニン１５３ｍｇ（白色固体、収率８２％）を得た。
^１Ｈ−ＮＭＲ（ＣＤＣｌ_３，４００ＭＨｚ）δ７．８７（ｄ，Ｊ＝８．２Ｈｚ，２Ｈ），７．６４（ｄ，Ｊ＝８．２Ｈｚ，２Ｈ），７．１３（ｄｄ，Ｊ＝７．２Ｈｚ，８．２Ｈｚ，２Ｈ），７．０５（ｄｄ，Ｊ＝０．８Ｈｚ，８．２Ｈｚ，２Ｈ），６．４１（ｄｄ，Ｊ＝０．８Ｈｚ，７．２Ｈｚ，２Ｈ），６．０４（ｓ，２Ｈ），１．３６（ｓ，１２Ｈ）。

Under argon atmosphere, 4.2 mg (0.015 mmol) of dichlorobis (trimethylphosphine) nickel, 2- (4-chlorophenyl) -2,3-dihydro-1H-naphtho [1,8-de] -1,3 in a reaction vessel. , 2-diazoborinine 139 mg (0.5 mmol), cesium fluoride 152 mg (1.0 mmol), 4,4,5,5,4 ′, 4 ′, 5 ′, 5′-octamethyl-2,2′-bi ( 1,3,2-dioxaborolanyl) 140 mg (0.55 mmol), trimethyl (2,2,2-trifluoroethoxy) silane 180 mg (1.05 mmol) and tetrahydrofuran 0.5 mL were added and sealed. Stir at 12 ° C. for 12 hours. After the reaction vessel was cooled to room temperature, 1 mL of a saturated aqueous ammonium chloride solution was added, followed by extraction three times with 8 mL of ethyl acetate, and the resulting organic phases were combined. The solvent was distilled off under reduced pressure, and the residue was purified using silica gel column chromatography (hexane: chloroform: ethyl acetate = 4: 1: 0 to 4: 1: 1) to give 2- [4- (4,4,4 5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) phenyl] -2,3-dihydro-1H-naphtho [1,8-de] -1,3,2-diazoborinine 153 mg (white solid Yield 82%).
¹ H-NMR (CDCl ₃ , 400 MHz) δ 7.87 (d, J = 8.2 Hz, 2H), 7.64 (d, J = 8.2 Hz, 2H), 7.13 (dd, J = 7. 2 Hz, 8.2 Hz, 2H), 7.05 (dd, J = 0.8 Hz, 8.2 Hz, 2H), 6.41 (dd, J = 0.8 Hz, 7.2 Hz, 2H), 6.04 (S, 2H), 1.36 (s, 12H).

  Example-36

アルゴン雰囲気下、反応容器にジクロロビス（トリメチルホスフィン）ニッケル４．２ｍｇ（０．０１５ｍｍｏｌ）、２−（２−クロロフェニル）−２，３−ジヒドロ−１Ｈ−ナフト［１，８−デ］−１，３，２−ジアゾボリニン１３９ｍｇ（０．５ｍｍｏｌ）、フッ化セシウム１５２ｍｇ（１．０ｍｍｏｌ）、４，４，５，５，４’，４’，５’，５’−オクタメチル−２，２’−ビ（１，３，２−ジオキサボロラニル）１４０ｍｇ（０．５５ｍｍｏｌ）、トリメチル（２，２，２−トリフルオロエトキシ）シラン１８０ｍｇ（１．０５ｍｍｏｌ）およびテトラヒドロフラン０．５ｍＬを加えて密閉し、１２０℃で３時間攪拌した。反応容器を室温まで冷却した後、飽和塩化アンモニウム水溶液１ｍＬを加え酢酸エチル８ｍＬで３回抽出し、得られた有機相を合わせた。溶媒を減圧留去し、残渣をシリカゲルカラムクロマトグラフィ（ヘキサン：クロロホルム：酢酸エチル＝４：１：０〜４：１：１）を用いて精製することにより、２−［２−（４，４，５，５−テトラメチル−１，３，２−ジオキサボロラン−２−イル）フェニル］−２，３−ジヒドロ−１Ｈ−ナフト［１，８−デ］−１，３，２−ジアゾボリニン１５８ｍｇ（白色固体、収率８６％）を得た。
^１Ｈ−ＮＭＲ（ＣＤＣｌ_３，４００ＭＨｚ）δ７．８２（ｄｄ，Ｊ＝１．０Ｈｚ，７．３Ｈｚ，１Ｈ），７．６３（ｄｄ，Ｊ＝１．０Ｈｚ，７．３Ｈｚ，１Ｈ），７．５０−７．４０（ｍ，２Ｈ），７．１２（ｄｄ，Ｊ＝７．３Ｈｚ，８．３Ｈｚ，２Ｈ），７．０２（ｄｄ，Ｊ＝０．８Ｈｚ，８．３Ｈｚ，２Ｈ），６．３９（ｓ，２Ｈ），６．３３（ｄｄ，Ｊ＝０．８Ｈｚ，７．３Ｈｚ，２Ｈ），１．３４（ｓ，１２Ｈ）。

Under argon atmosphere, 4.2 mg (0.015 mmol) of dichlorobis (trimethylphosphine) nickel, 2- (2-chlorophenyl) -2,3-dihydro-1H-naphtho [1,8-de] -1,3 in a reaction vessel. , 2-diazoborinine 139 mg (0.5 mmol), cesium fluoride 152 mg (1.0 mmol), 4,4,5,5,4 ′, 4 ′, 5 ′, 5′-octamethyl-2,2′-bi ( 1,3,2-dioxaborolanyl) 140 mg (0.55 mmol), trimethyl (2,2,2-trifluoroethoxy) silane 180 mg (1.05 mmol) and tetrahydrofuran 0.5 mL were added and sealed. Stir at 0 ° C. for 3 hours. After the reaction vessel was cooled to room temperature, 1 mL of a saturated aqueous ammonium chloride solution was added, followed by extraction three times with 8 mL of ethyl acetate, and the resulting organic phases were combined. The solvent was distilled off under reduced pressure, and the residue was purified using silica gel column chromatography (hexane: chloroform: ethyl acetate = 4: 1: 0 to 4: 1: 1) to give 2- [2- (4,4,4 5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) phenyl] -2,3-dihydro-1H-naphtho [1,8-de] -1,3,2-diazoborinine 158 mg (white solid Yield 86%).
¹ H-NMR (CDCl ₃ , 400 MHz) δ 7.82 (dd, J = 1.0 Hz, 7.3 Hz, 1 H), 7.63 (dd, J = 1.0 Hz, 7.3 Hz, 1 H), 7. 50-7.40 (m, 2H), 7.12 (dd, J = 7.3 Hz, 8.3 Hz, 2H), 7.02 (dd, J = 0.8 Hz, 8.3 Hz, 2H), 6 .39 (s, 2H), 6.33 (dd, J = 0.8 Hz, 7.3 Hz, 2H), 1.34 (s, 12H).

  Example-37

アルゴン雰囲気下、反応容器にジクロロビス（トリメチルホスフィン）ニッケル４．２ｍｇ（０．０１５ｍｍｏｌ）、２−（３−クロロー４−フルオロフェニル）−２，３−ジヒドロ−１Ｈ−ナフト［１，８−デ］−１，３，２−ジアゾボリニン１４９ｍｇ（０．５ｍｍｏｌ）、フッ化セシウム１５２ｍｇ（１．０ｍｍｏｌ）、４，４，５，５，４’，４’，５’，５’−オクタメチル−２，２’−ビ（１，３，２−ジオキサボロラニル）１４０ｍｇ（０．５５ｍｍｏｌ）、トリメチル（２，２，２−トリフルオロエトキシ）シラン１８０ｍｇ（１．０５ｍｍｏｌ）およびテトラヒドロフラン０．５ｍＬを加えて密閉し、１２０℃で３時間攪拌した。反応容器を室温まで冷却した後、飽和塩化アンモニウム水溶液１ｍＬを加え酢酸エチル８ｍＬで３回抽出し、得られた有機相を合わせた。溶媒を減圧留去し、残渣をシリカゲルカラムクロマトグラフィ（ヘキサン：クロロホルム：酢酸エチル＝４：１：０〜４：１：１）を用いて精製することにより、２−［４−フルオロ−３−（４，４，５，５−テトラメチル−１，３，２−ジオキサボロラン−２−イル）フェニル］−２，３−ジヒドロ−１Ｈ−ナフト［１，８−デ］−１，３，２−ジアゾボリニン１６５ｍｇ（白色固体、収率８５％）を得た。
^１Ｈ−ＮＭＲ（ＣＤＣｌ_３，４００ＭＨｚ）δ８．０２（ｄｄ，Ｊ＝２．０Ｈｚ，６．２Ｈｚ，１Ｈ），７．７２（ｄｄｄ，Ｊ＝２．０Ｈｚ，５．８Ｈｚ，７．８Ｈｚ，１Ｈ），７．１６−７．０４（ｍ，５Ｈ），６．４３（ｄｄ，Ｊ＝０．８Ｈｚ，７．２Ｈｚ，２Ｈ），６．０４（ｓ，２Ｈ），１．４０（ｓ，１２Ｈ）．
^１９Ｆ−ＮＭＲ（ＣＤＣｌ_３，３７６ＭＨｚ）δ−９９．５（ｓ，１Ｆ）。

Under an argon atmosphere, 4.2 mg (0.015 mmol) of dichlorobis (trimethylphosphine) nickel, 2- (3-chloro-4-fluorophenyl) -2,3-dihydro-1H-naphtho [1,8-de] in a reaction vessel. -1,3,2-diazoborinine 149 mg (0.5 mmol), cesium fluoride 152 mg (1.0 mmol), 4,4,5,5,4 ′, 4 ′, 5 ′, 5′-octamethyl-2,2 Adding 140 mg (0.55 mmol) of '-bi (1,3,2-dioxaborolanyl), 180 mg (1.05 mmol) of trimethyl (2,2,2-trifluoroethoxy) silane and 0.5 mL of tetrahydrofuran Sealed and stirred at 120 ° C. for 3 hours. After the reaction vessel was cooled to room temperature, 1 mL of a saturated aqueous ammonium chloride solution was added, followed by extraction three times with 8 mL of ethyl acetate, and the resulting organic phases were combined. The solvent was distilled off under reduced pressure, and the residue was purified using silica gel column chromatography (hexane: chloroform: ethyl acetate = 4: 1: 0 to 4: 1: 1) to give 2- [4-fluoro-3- ( 4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) phenyl] -2,3-dihydro-1H-naphtho [1,8-de] -1,3,2-diazoborinine 165 mg (white solid, 85% yield) was obtained.
¹ H-NMR (CDCl ₃ , 400 MHz) δ 8.02 (dd, J = 2.0 Hz, 6.2 Hz, 1H), 7.72 (ddd, J = 2.0 Hz, 5.8 Hz, 7.8 Hz, 1H) ), 7.16-7.04 (m, 5H), 6.43 (dd, J = 0.8 Hz, 7.2 Hz, 2H), 6.04 (s, 2H), 1.40 (s, 12H) ).
¹⁹ F-NMR (CDCl ₃ , 376 MHz) δ-99.5 (s, 1F).

  Example-38

アルゴン雰囲気下、反応容器にジクロロビス（トリメチルホスフィン）ニッケル４．２ｍｇ（０．０１５ｍｍｏｌ）、１−クロロナフタレン８０．５ｍｇ（０．５ｍｍｏｌ）、フッ化セシウム１５２ｍｇ（１．０ｍｍｏｌ）、４，４，５，５，４’，４’，５’，５’−オクタメチル−２，２’−ビ（１，３，２−ジオキサボロラニル）１５３ｍｇ（０．６ｍｍｏｌ）、トリメチル（２，２，２−トリフルオロエトキシ）シラン１８０ｍｇ（１．０５ｍｍｏｌ）およびテトラヒドロフラン０．５ｍＬを加えて密閉し、１００℃で２時間攪拌した。反応容器を室温まで冷却した後、飽和塩化アンモニウム水溶液１ｍＬを加え酢酸エチル８ｍＬで３回抽出し、得られた有機相を合わせた。溶媒を減圧留去し、残渣をシリカゲルカラムクロマトグラフィ（ヘキサン：クロロホルム：酢酸エチル＝１６：４：０〜１６：４：１）を用いて精製することにより、２−（１−ナフチル）−４，４，５，５−テトラメチル−１，３，２−ジオキサボロラン１０１ｍｇ（白色固体、収率８０％）を得た。
^１Ｈ−ＮＭＲ（ＣＤＣｌ_３，４００ＭＨｚ）δ８．７６（ｄ，Ｊ＝８．２Ｈｚ，１Ｈ），８．０７（ｄｄ，Ｊ＝１．３Ｈｚ，６．８Ｈｚ，１Ｈ），７．９３（ｄ，Ｊ＝８．２Ｈｚ，１Ｈ），７．８３（ｄｄ，Ｊ＝１．３Ｈｚ，８．０Ｈｚ，１Ｈ），７．５５−７．４５（ｍ，３Ｈ），１．４３（ｓ，１２Ｈ）。

Under an argon atmosphere, 4.2 mg (0.015 mmol) of dichlorobis (trimethylphosphine) nickel, 80.5 mg (0.5 mmol) of 1-chloronaphthalene, 152 mg (1.0 mmol) of cesium fluoride, 4, 4, 5 , 5,4 ′, 4 ′, 5 ′, 5′-octamethyl-2,2′-bi (1,3,2-dioxaborolanyl), 153 mg (0.6 mmol), trimethyl (2,2,2) -Trifluoroethoxy) silane (180 mg, 1.05 mmol) and tetrahydrofuran (0.5 mL) were added and sealed, followed by stirring at 100 ° C. for 2 hours. After the reaction vessel was cooled to room temperature, 1 mL of a saturated aqueous ammonium chloride solution was added, followed by extraction three times with 8 mL of ethyl acetate, and the resulting organic phases were combined. The solvent was distilled off under reduced pressure, and the residue was purified using silica gel column chromatography (hexane: chloroform: ethyl acetate = 16: 4: 0 to 16: 4: 1) to give 2- (1-naphthyl) -4, 101 mg (white solid, yield 80%) of 4,5,5-tetramethyl-1,3,2-dioxaborolane was obtained.
¹ H-NMR (CDCl ₃ , 400 MHz) δ 8.76 (d, J = 8.2 Hz, 1H), 8.07 (dd, J = 1.3 Hz, 6.8 Hz, 1H), 7.93 (d, J = 8.2 Hz, 1H), 7.83 (dd, J = 1.3 Hz, 8.0 Hz, 1H), 7.55-7.45 (m, 3H), 1.43 (s, 12H).

  Example-39

アルゴン雰囲気下、反応容器にジクロロビス（トリメチルホスフィン）ニッケル２．８ｍｇ（０．０１ｍｍｏｌ）、２−クロロナフタレン８１．５ｍｇ（０．５ｍｍｏｌ）、フッ化セシウム１５２ｍｇ（１．０ｍｍｏｌ）、４，４，５，５，４’，４’，５’，５’−オクタメチル−２，２’−ビ（１，３，２−ジオキサボロラニル）１４０ｍｇ（０．５５ｍｍｏｌ）、トリメチル（２，２，２−トリフルオロエトキシ）シラン１８０ｍｇ（１．０５ｍｍｏｌ）およびテトラヒドロフラン０．５ｍＬを加えて密閉し、１００℃で２時間攪拌した。反応容器を室温まで冷却した後、飽和塩化アンモニウム水溶液１ｍＬを加え酢酸エチル８ｍＬで３回抽出し、得られた有機相を合わせた。溶媒を減圧留去し、残渣をシリカゲルカラムクロマトグラフィ（ヘキサン：クロロホルム：酢酸エチル＝１６：４：０〜１６：４：１）を用いて精製することにより、２−（２−ナフチル）−４，４，５，５−テトラメチル−１，３，２−ジオキサボロラン１０４ｍｇ（白色固体、収率８２％）を得た。
^１Ｈ−ＮＭＲ（ＣＤＣｌ_３，４００ＭＨｚ）δ８．３７（ｓ，１Ｈ），７．８９−７．８１（ｍ，４Ｈ），７．５３−７．４５（ｍ，２Ｈ），１．３９（ｓ，１２Ｈ）。

Under an argon atmosphere, 2.8 mg (0.01 mmol) of dichlorobis (trimethylphosphine) nickel, 81.5 mg (0.5 mmol) of 2-chloronaphthalene, 152 mg (1.0 mmol) of cesium fluoride, 4, 4, 5 , 5,4 ′, 4 ′, 5 ′, 5′-octamethyl-2,2′-bi (1,3,2-dioxaborolanyl) 140 mg (0.55 mmol), trimethyl (2,2,2) -Trifluoroethoxy) silane (180 mg, 1.05 mmol) and tetrahydrofuran (0.5 mL) were added and sealed, followed by stirring at 100 ° C. for 2 hours. After the reaction vessel was cooled to room temperature, 1 mL of a saturated aqueous ammonium chloride solution was added, followed by extraction three times with 8 mL of ethyl acetate, and the resulting organic phases were combined. The solvent was distilled off under reduced pressure, and the residue was purified using silica gel column chromatography (hexane: chloroform: ethyl acetate = 16: 4: 0 to 16: 4: 1) to give 2- (2-naphthyl) -4, 104 mg (white solid, yield 82%) of 4,5,5-tetramethyl-1,3,2-dioxaborolane was obtained.
¹ H-NMR (CDCl ₃ , 400 MHz) δ 8.37 (s, 1H), 7.89-7.81 (m, 4H), 7.53-7.45 (m, 2H), 1.39 (s , 12H).

  Example-40

アルゴン雰囲気下、反応容器にジクロロビス（トリメチルホスフィン）ニッケル７．０ｍｇ（０．０２５ｍｍｏｌ）、４−クロロアニソール７０．２ｍｇ（０．５ｍｍｏｌ）、フッ化セシウム１５２ｍｇ（１．０ｍｍｏｌ）、４，４，６，４’，４’，６’−ヘキサメチル−２，２’−ビ（１，３，２−ジオキサボロリナリル）１４０ｍｇ（０．５５ｍｍｏｌ）、トリメチル（２，２，２−トリフルオロエトキシ）シラン１８０ｍｇ（１．０５ｍｍｏｌ）およびテトラヒドロフラン０．５ｍＬを加えて密閉し、１００℃で２時間攪拌した。反応容器を室温まで冷却した後、飽和塩化アンモニウム水溶液１ｍＬを加え酢酸エチル８ｍＬで３回抽出し、得られた有機相を合わせた。溶媒を減圧留去し、残渣をシリカゲルカラムクロマトグラフィ（ヘキサン：クロロホルム：酢酸エチル＝１６：４：０〜１６：４：１）を用いて精製することにより、２−（４−メトキシフェニル）−４，４，６−トリメチル−１，３，２−ジオキサボリナン１０７ｍｇ（無色液体、収率９３％）を得た。
^１Ｈ−ＮＭＲ（ＣＤＣｌ_３，４００ＭＨｚ）δ７．７５（ｄ，Ｊ＝８．４Ｈｚ，２Ｈ），６．８６（ｄ，Ｊ＝８．４Ｈｚ，２Ｈ），４．３１（ｄｄｑ，Ｊ＝３．０Ｈｚ，６．０Ｈｚ，１１．９Ｈｚ，１Ｈ），３．８０（ｓ，３Ｈ），１．８３（ｄｄ，Ｊ＝３．０Ｈｚ，１３．８Ｈｚ，１Ｈ），１．５６（ｄｄ，Ｊ＝１１．９Ｈｚ，１３．８Ｈｚ，１Ｈ），１．３５（ｓ，３Ｈ），１．３４（ｓ，３Ｈ），１．３２（ｄ，Ｊ＝６．０Ｈｚ，３Ｈ）。

Under argon atmosphere, dichlorobis (trimethylphosphine) nickel 7.0 mg (0.025 mmol), 4-chloroanisole 70.2 mg (0.5 mmol), cesium fluoride 152 mg (1.0 mmol), 4, 4, 6 , 4 ′, 4 ′, 6′-hexamethyl-2,2′-bi (1,3,2-dioxaborolinalyl) 140 mg (0.55 mmol), trimethyl (2,2,2-trifluoroethoxy) silane 180 mg (1.05 mmol) and 0.5 mL of tetrahydrofuran were added and sealed, followed by stirring at 100 ° C. for 2 hours. After the reaction vessel was cooled to room temperature, 1 mL of a saturated aqueous ammonium chloride solution was added, followed by extraction three times with 8 mL of ethyl acetate, and the resulting organic phases were combined. The solvent was distilled off under reduced pressure, and the residue was purified using silica gel column chromatography (hexane: chloroform: ethyl acetate = 16: 4: 0 to 16: 4: 1) to give 2- (4-methoxyphenyl) -4. , 4,6-trimethyl-1,3,2-dioxaborinane (107 mg, colorless liquid, yield 93%) was obtained.
¹ H-NMR (CDCl ₃ , 400 MHz) δ 7.75 (d, J = 8.4 Hz, 2H), 6.86 (d, J = 8.4 Hz, 2H), 4.31 (ddq, J = 3. 0 Hz, 6.0 Hz, 11.9 Hz, 1H), 3.80 (s, 3H), 1.83 (dd, J = 3.0 Hz, 13.8 Hz, 1H), 1.56 (dd, J = 11 .9 Hz, 13.8 Hz, 1H), 1.35 (s, 3H), 1.34 (s, 3H), 1.32 (d, J = 6.0 Hz, 3H).

  Example-41

アルゴン雰囲気下、反応容器にジクロロビス（トリメチルホスフィン）ニッケル１．４ｍｇ（０．００５ｍｍｏｌ）、４−クロロ安息香酸メチル８５．０ｍｇ（０．５ｍｍｏｌ）、リン酸カリウム２１２ｍｇ（１．０ｍｍｏｌ）、２，２，２−トリフルオロエタノール２５ｍｇ（０．２５ｍｍｏｌ）、４，４，５，５，４’，４’，５’，５’−オクタメチル−２，２’−ビ（１，３，２−ジオキサボロラニル）１４０ｍｇ（０．５５ｍｍｏｌ）およびトルエン１．０ｍＬを加えて密閉し、１００℃で１２時間攪拌した。反応容器を室温まで冷却した後、飽和塩化アンモニウム水溶液１ｍＬ、酢酸エチル８ｍＬを加えた後、ガスクロマトグラフィーを用いて分析することにより、４−（４，４，５，５−テトラメチル−１，３，２−ジオキサボロラン−２−イル）安息香酸メチルの生成を確認した（ＧＣ収率９０％）。

Under argon atmosphere, dichlorobis (trimethylphosphine) nickel 1.4 mg (0.005 mmol), methyl 4-chlorobenzoate 85.0 mg (0.5 mmol), potassium phosphate 212 mg (1.0 mmol), 2, 2 , 2-trifluoroethanol 25 mg (0.25 mmol), 4,4,5,5,4 ′, 4 ′, 5 ′, 5′-octamethyl-2,2′-bi (1,3,2-dioxa Borolanyl) (140 mg, 0.55 mmol) and toluene (1.0 mL) were added and sealed, and the mixture was stirred at 100 ° C. for 12 hours. After cooling the reaction vessel to room temperature, 1 mL of a saturated aqueous ammonium chloride solution and 8 mL of ethyl acetate were added, and then analyzed by gas chromatography to obtain 4- (4,4,5,5-tetramethyl-1, Formation of methyl 3,2-dioxaborolan-2-yl) benzoate was confirmed (GC yield 90%).

  Example-42

アルゴン雰囲気下、反応容器にジクロロビス（トリメチルホスフィン）ニッケル７．０ｍｇ（０．０２５ｍｍｏｌ）、２−クロロ−４，６−ジフルオロアニリン８１．６ｍｇ（０．５ｍｍｏｌ）、フッ化セシウム１５２ｍｇ（１．０ｍｍｏｌ）、４，４，５，５，４’，４’，５’，５’−オクタメチル−２，２’−ビ（１，３，２−ジオキサボロラニル）１４０ｍｇ（０．５５ｍｍｏｌ）、トリメチル（２，２，２−トリフルオロエトキシ）シラン１８０ｍｇ（１．０５ｍｍｏｌ）、テトラヒドロフラン０．５ｍＬを加えて密閉し、１００℃で１２時間攪拌した。反応容器を室温まで冷却した後、飽和塩化アンモニウム水溶液１ｍＬを加え酢酸エチル８ｍＬで３回抽出し、得られた有機相を合わせた。減圧蒸留（１１５−１２０度、１．５ｍｍＨｇ）することにより、２，４−ジフルオロ−６−（４，４，５，５−テトラメチル−１，３，２−ジオキサボロラン−２−イル）アニリン１０５ｍｇ（白色固体、収率８２％）を得た。
^１Ｈ−ＮＭＲ（ＣＤＣｌ_３，４００ＭＨｚ）δ７．１０（ｄｄｄ，Ｊ＝１．４Ｈｚ，２．９Ｈｚ，８．７Ｈｚ，１Ｈ），６．８４（ｄｄｄ，Ｊ＝２．９Ｈｚ，８．３Ｈｚ，１１．２Ｈｚ，１Ｈ），４．６４（ｓ，２Ｈ），１．３４（ｓ，１２Ｈ）．
^１９Ｆ−ＮＭＲ（ＣＤＣｌ_３，３７６ＭＨｚ）δ−１２６．４（ｓ，１Ｆ），−１３２．１（ｓ，１Ｆ）。

Under an argon atmosphere, 7.0 mg (0.025 mmol) of dichlorobis (trimethylphosphine) nickel, 81.6 mg (0.5 mmol) of 2-chloro-4,6-difluoroaniline, 152 mg (1.0 mmol) of cesium fluoride were placed in a reaction vessel. 4,4,5,5,4 ′, 4 ′, 5 ′, 5′-octamethyl-2,2′-bi (1,3,2-dioxaborolanyl) 140 mg (0.55 mmol), trimethyl 180 mg (1.05 mmol) of (2,2,2-trifluoroethoxy) silane and 0.5 mL of tetrahydrofuran were added and sealed, followed by stirring at 100 ° C. for 12 hours. After the reaction vessel was cooled to room temperature, 1 mL of a saturated aqueous ammonium chloride solution was added, followed by extraction three times with 8 mL of ethyl acetate, and the resulting organic phases were combined. By distillation under reduced pressure (115-120 degrees, 1.5 mmHg), 2,4-difluoro-6- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) aniline 105 mg (White solid, yield 82%) was obtained.
¹ H-NMR (CDCl ₃ , 400 MHz) δ 7.10 (ddd, J = 1.4 Hz, 2.9 Hz, 8.7 Hz, 1 H), 6.84 (ddd, J = 2.9 Hz, 8.3 Hz, 11 .2 Hz, 1H), 4.64 (s, 2H), 1.34 (s, 12H).
¹⁹ F-NMR (CDCl ₃ , 376 MHz) δ-126.4 (s, 1F), -132.1 (s, 1F).

  Example-43

アルゴン雰囲気下、反応容器にジクロロビス（トリメチルホスフィン）ニッケル４．２ｍｇ（０．０１５ｍｍｏｌ）、２−クロロアニリン６３．３ｍｇ（０．５ｍｍｏｌ）、フッ化セシウム１５２ｍｇ（１．０ｍｍｏｌ）、４，４，５，５，４’，４’，５’，５’−オクタメチル−２，２’−ビ（１，３，２−ジオキサボロラニル）１４０ｍｇ（０．５５ｍｍｏｌ）、トリメチル（２，２，２−トリフルオロエトキシ）シラン１８０ｍｇ（１．０５ｍｍｏｌ）およびテトラヒドロフラン０．５ｍＬを加えて密閉し、１００℃で１２時間攪拌した。反応容器を室温まで冷却した後、飽和塩化アンモニウム水溶液１ｍＬを加え酢酸エチル８ｍＬで３回抽出し、得られた有機相を合わせた。減圧蒸留（１２５−１３０℃、１．５ｍｍＨｇ）することにより、２−（４，４，５，５−テトラメチル−１，３，２−ジオキサボロラン−２−イル）アニリン８７ｍｇ（白色固体、収率８０％）を得た。
^１Ｈ−ＮＭＲ（ＣＤＣｌ_３，４００ＭＨｚ）δ７．６１（ｄｄ，Ｊ＝１．７Ｈｚ，７．３Ｈｚ，１Ｈ），７．２１（ｄｄｄ，Ｊ＝１．７Ｈｚ，７．３Ｈｚ，８．２Ｈｚ，１Ｈ），６．６７（ｄｄｄ，Ｊ＝１．０Ｈｚ，７．３Ｈｚ，７．３Ｈｚ，１Ｈ），６．５９（ｄ，Ｊ＝８．２Ｈｚ，１Ｈ），４．７１（ｓ，２Ｈ），１．３４（ｓ，１２Ｈ）。

Under an argon atmosphere, 4.2 mg (0.015 mmol) of dichlorobis (trimethylphosphine) nickel, 63.3 mg (0.5 mmol) of 2-chloroaniline, 152 mg (1.0 mmol) of cesium fluoride, 4, 4, 5 , 5,4 ′, 4 ′, 5 ′, 5′-octamethyl-2,2′-bi (1,3,2-dioxaborolanyl) 140 mg (0.55 mmol), trimethyl (2,2,2) -Trifluoroethoxy) silane (180 mg, 1.05 mmol) and tetrahydrofuran (0.5 mL) were added and sealed, followed by stirring at 100 ° C. for 12 hours. After the reaction vessel was cooled to room temperature, 1 mL of a saturated aqueous ammonium chloride solution was added, followed by extraction three times with 8 mL of ethyl acetate, and the resulting organic phases were combined. By vacuum distillation (125-130 ° C., 1.5 mmHg), 87 mg of 2- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) aniline (white solid, yield) 80%).
¹ H-NMR (CDCl ₃ , 400 MHz) δ 7.61 (dd, J = 1.7 Hz, 7.3 Hz, 1H), 7.21 (ddd, J = 1.7 Hz, 7.3 Hz, 8.2 Hz, 1H) ), 6.67 (ddd, J = 1.0 Hz, 7.3 Hz, 7.3 Hz, 1H), 6.59 (d, J = 8.2 Hz, 1H), 4.71 (s, 2H), 1 .34 (s, 12H).

  Example-44

アルゴン雰囲気下、反応容器にジクロロビス（トリメチルホスフィン）ニッケル４．２ｍｇ（０．０１５ｍｍｏｌ）、２−クロロ−４−シアノアニリン６３．３ｍｇ（０．５ｍｍｏｌ）、フッ化セシウム１５２ｍｇ（１．０ｍｍｏｌ）、４，４，５，５，４’，４’，５’，５’−オクタメチル−２，２’−ビ（１，３，２−ジオキサボロラニル）１４０ｍｇ（０．５５ｍｍｏｌ）、トリメチル（２，２，２−トリフルオロエトキシ）シラン１８０ｍｇ（１．０５ｍｍｏｌ）およびテトラヒドロフラン０．５ｍＬを加えて密閉し、１００℃で２時間攪拌した。反応容器を室温まで冷却した後、飽和塩化アンモニウム水溶液１ｍＬを加え酢酸エチル８ｍＬで３回抽出し、得られた有機相を合わせた。減圧蒸留（１７０−１７５℃、３ｍｍＨｇ）することにより、４−シアノ−２−（４，４，５，５−テトラメチル−１，３，２−ジオキサボロラン−２−イル）アニリン１０１ｍｇ（白色固体、収率８３％）を得た。
^１Ｈ−ＮＭＲ（ＣＤＣｌ_３，４００ＭＨｚ）δ７．８９（ｄ，Ｊ＝１．９Ｈｚ，１Ｈ），７．４１（ｄｄ，Ｊ＝１．９Ｈｚ，８．５Ｈｚ，１Ｈ），６．５５（ｄ，Ｊ＝８．５Ｈｚ，１Ｈ），５．２８（ｓ，２Ｈ），１．３４（ｓ，１２Ｈ）。

Under argon atmosphere, dichlorobis (trimethylphosphine) nickel 4.2 mg (0.015 mmol), 2-chloro-4-cyanoaniline 63.3 mg (0.5 mmol), cesium fluoride 152 mg (1.0 mmol), 4 , 4,5,5,4 ′, 4 ′, 5 ′, 5′-octamethyl-2,2′-bi (1,3,2-dioxaborolanyl) 140 mg (0.55 mmol), trimethyl (2 , 2,2-trifluoroethoxy) silane 180 mg (1.05 mmol) and tetrahydrofuran 0.5 mL were added and sealed, and the mixture was stirred at 100 ° C. for 2 hours. After the reaction vessel was cooled to room temperature, 1 mL of a saturated aqueous ammonium chloride solution was added, followed by extraction three times with 8 mL of ethyl acetate, and the resulting organic phases were combined. By distillation under reduced pressure (170-175 ° C., 3 mmHg), 101 mg of 4-cyano-2- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) aniline (white solid, Yield 83%) was obtained.
¹ H-NMR (CDCl ₃ , 400 MHz) δ 7.89 (d, J = 1.9 Hz, 1H), 7.41 (dd, J = 1.9 Hz, 8.5 Hz, 1H), 6.55 (d, J = 8.5 Hz, 1H), 5.28 (s, 2H), 1.34 (s, 12H).

Claims (3)

General formula (1)

(Wherein A represents an ethylene group or trimethylene group which may be substituted with a methyl group) and a general formula (2)

(Wherein R ¹ represents a fluorine atom; a fluorine atom or an alkyl group having 1 to 8 carbon atoms which may be substituted with a fluorine atom or an alkoxy group having 1 to 4 carbon atoms; (alkoxy having 1 to 4 carbon atoms) carbonyl group; An alkoxy group having 1 to 4 carbon atoms which may be substituted with a chlorine atom; an alkenyl group having 2 to 4 carbon atoms; an amino group which may be substituted with an acyl group having 2 to 9 carbon atoms; A morpholino group, a phenylcarbonyl group, a cyano group, a carbamoyl group, a 2,3-dihydro-1H-naphtho [1,8-de] -1,3,2-diazoborinyl group, and adjacent R ¹ groups. May form an aromatic hydrocarbon ring together with the carbon to be bonded, m represents an integer of 0 to 5. When m is 2 to 5, R ¹ is the same or different. Chlorobenzene derivative represented by Are reacted, the general formula (3)

(Wherein A, R ¹ and m represent the same contents as described above), the trimethylphosphine coordinated nickel catalyst and the general formula (4)

(In the formula, R ² represents a hydrogen atom or a fluorine atom. R ³ and R ⁴ each independently represents a hydrogen atom or a methyl group. M represents an alkali metal atom. N represents 1 to 11). A method for producing phenylboronic acid esters, characterized by using an alkoxide represented by: The production method according to claim 1, wherein the trimethylphosphine coordinated nickel catalyst is dichlorobis (trimethylphosphine) nickel. The production method according to claim 1 or 2, wherein the alkali metal atom is potassium, rubidium or cesium.