JP7223445B2 - 脱離基を有する有機化合物と有機ケイ素化合物とのカップリング体の製造方法 - Google Patents
脱離基を有する有機化合物と有機ケイ素化合物とのカップリング体の製造方法 Download PDFInfo
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Description
Ar1-X …(1)
[式(1)中、Ar1は置換されていてもよいアリール基又は置換されていてもよいヘテロアリール基を示し、Xは臭素原子、ヨウ素原子、メタンスルホニルオキシ基及びトリフルオロメタンスルホニルオキシ基から選ばれる脱離基を示す。]
Ar2-Si(OR)3 …(2)
[式(2)中、Ar2は置換されていてもよいアリール基、置換されていてもよいヘテロアリール基又は置換されていてもよいビニル基を示し、Rは炭素数1~5のアルキル基を示す。なお、複数存在するRは、それぞれ同一でも異なっていてもよい。]
Ar1-Ar2 …(3)
[式(3)中、Ar1及びAr2は上記と同義である。]
まず、上記アルコール溶媒と一般式(2)で表される化合物とが、上記無機塩基の存在下で反応することにより、下記式(α)で表される中間体を形成する。この中間体が、従来の檜山反応における中間体よりも活性が高いために、一般式(1)で表される化合物との反応が円滑に進行するため、使用するパラジウム触媒の量を減らした場合であっても、良好な収率で檜山反応のカップリング体を得ることができると本発明者等は推察している。なお、式(α)で表される中間体は、上記アルコール溶媒として、プロピレングリコールを用いた場合の例であり、M+は無機塩基由来の金属イオンを示す。
下記反応式(A)に従って、種々溶媒を変更した他は、同様の条件で、パラジウム錯体(3)及びフッ化カリウム(KF)の存在下、4-ブロモトルエン(1a)とトリメトキシフェニルシラン(2a)とのカップリング反応を行い、目的のカップリング体(4a)を得た。具体的な操作を以下に示す。
用いる塩基を表2に示すように変更した他は、実施例2と同様にして、反応を行った(下記反応式(B)参照)。その結果を表2に示す。
触媒量及び反応温度を表3に示すように変更した他は、実施例2と同様にして、反応を行った(下記反応式(C)参照)。その結果を表3に示す。
パラジウム(Pd)触媒を以下に示すように変更した他は、実施例10と同様にして、反応を行った(下記反応式(D)参照)。その結果を以下に示す。具体的には、実施例毎に、用いたPd触媒を、反応率(conv.)(%)及びカップリング体(4a)の収率(yield)(%)とともに以下に示す。
実施例10:G. Hamasaka, F. Sakurai, Y. Uozumi, Chem. Commun. 2015, 51, 3886.
実施例11:F. Ragaini, M. Gasperini, S. Cenini, L. Arnera, A. Caselli, P.Macchi, N. Casati, Chem. Eur. J. 2009, 15, 8064.
実施例12:Newkome, G. R.; Pantaleo, D. C.; Puckett, W. E.; Ziefle, P. L.;Deutsch, W. A. J. Inorg. Nucl. Chem. 1981, 43, 1529.
実施例13:K. Takenaka, M. Minakawa, Y. Uozumi. J. Am. Chem. Soc. 2005, 127,12273.
用いる基質(1)を変更した他は、実施例10と同様にして、反応を行った(下記反応式(E)参照)。その結果を以下に示す。具体的には、実施例毎に、得られたカップリング体(4’)の構造を、その収率(%)とともに以下に示す。なお、構造中、点線よりも左側が基質(1)由来の基であり、右側が基質(2a)由来の基である(以下、同様)。
用いる基質(2’)をそれぞれ変更した他は、実施例10と同様にして、反応を行った(下記反応式(F)参照)。その結果を以下に示す。具体的には、実施例毎に、得られたカップリング体(4”)の構造を、その収率(%)とともに以下に示す。
ニキビ治療薬の有効成分であるアダパレンの合成を実施した(下記反応式(G)参照)。具体的な実験操作を以下に示す。
テフロン(登録商標)被覆した攪拌子が入っている大型試験管へ、フッ化カリウム(KF)(3.1g,54.0mmol)と6-ブロモ-2-ナフタレンカルボン酸(1b)(4.5g,18.0mmol)を入れ、プロピレングリコール(36mL)を加えた。トリエトキシシラン誘導体(2b)(8.7g,21.6mmol)を反応容器へと加えた。
パラジウム触媒(3)(0.23mg,1.0×10-3mmol)をジクロロメチレン(1mL)へと溶解させた。この溶液(0.18mL,5mol ppmPd)を反応溶液へと加え、100℃で12時間加熱攪拌した。加熱終了後、水(36mL)を加え、室温下10分間攪拌した。得られた反応混合物をセライト上で、水、tert-ブチルメチルエーテルを用い、洗浄した。テトラヒドロフランを用い、固体上に残った生成物を溶出させた。減圧下、揮発性有機物を留去することで、アダパレンを6.9g、93%単離収率で得た。
用いる基質(1)及び基質(2)をそれぞれ変更し、且つ触媒量を100mol ppmとした他は、実施例10と同様にして、反応を行った(下記反応式(H)参照)。その結果を以下に示す。具体的には、実施例毎に、得られたカップリング体(4)の構造を、その収率(%)とともに以下に示す。
用いる基質を4-ブロモトルエン(1a)から4-ヨードトルエン(1c)に変更した他は、実施例10と同様にして、反応を行った(下記反応式(I)参照)。その結果、収率87%で目的のカップリング体(4a)が得られた。
用いる基質を基質(1d)及び基質(2c)に変更した他は、実施例10と同様にして、反応を行った(下記反応式(J)参照)。その結果、収率90%で目的のデキストロメトルファン誘導体が得られた。なお、デキストロメトルファンは、鎮咳去痰薬の一種である。
用いる基質を基質(1e)及び基質(2d)に変更した他は、実施例10と同様にして、反応を行った(下記反応式(k)参照)。その結果、収率88%で目的の液晶化合物が得られた。
Claims (1)
- 隣接した2つの炭素原子がそれぞれ水酸基を有する部位を含むアルコール溶媒、無機塩基及びパラジウム触媒の存在下、下記一般式(1)で表される化合物と下記一般式(2)で表される化合物とを反応させて、下記一般式(3)で表されるカップリング体を得る、カップリング体の製造方法であって、
前記パラジウム触媒が以下に示すパラジウム触媒から選ばれる、製造方法。
Ar1-X…(1)
[式(1)中、Ar1は置換されていてもよいアリール基又は置換されていてもよいヘテロアリール基を示し、Xは臭素原子、ヨウ素原子、メタンスルホニルオキシ基及びトリフルオロメタンスルホニルオキシ基から選ばれる脱離基を示す。]
Ar2-Si(OR)3…(2)
[式(2)中、Ar2は置換されていてもよいアリール基、置換されていてもよいヘテロアリール基又は置換されていてもよいビニル基を示し、Rは炭素数1~5のアルキル基を示す。]
Ar1-Ar2…(3)
[式(3)中、Ar1及びAr2は上記と同義である。]
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BLASZCZYK, Izabela et al.,Orthometallated palladium trimers in C-C coupling reactions,Journal of Organometallic Chemistry,2012年,Vol.710,pp.44-52 |
BLASZCZYK, Izabela et al.,Suzuki-Miyaura and Hiyama reactions catalyzed by orthopalladated triarylphosphite complexes,Tetrahedron,2010年,Vol.66,pp.9502-9507 |
GORDILLO A. et al,Consecutive palladium-catalyzed Hiyama-Heck reactions in aqueous media under ligand-free conditions,Chemical Communications(Cambridge, United Kingdom),2007年,No.39,pp.4056-4058 |
HAMASAKA, Go et al.,A palladium NNC-pincer complex: an efficient catalyst for allylic arylation at parts per billion lev,ChemCommun.,2015年,Vol.51,pp.3886-3888 |
SHI S. et al.,Pd(OAc)2-Catalyzed Fluoride-Free Cross-Coupling Reactions of Arylsiloxanes with Aryl Bromides in Aqu,Journal of Organic Chemistry,2007年,Vol.72,No.15,pp.5927-5930 |
SRIMANI, D. et al.,Convenient systhesis of palladium nanoparticles and catalysis of hiyama coupling reaction in water,ORGANIC LETTERS,2007年,Vol.9, No.18,pp.3639-3642,DOI:10.1021/ol7015143 |
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