JP2020138947A - Optically active benzazaborole derivative and method for producing the same - Google Patents

Optically active benzazaborole derivative and method for producing the same Download PDF

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JP2020138947A
JP2020138947A JP2019037114A JP2019037114A JP2020138947A JP 2020138947 A JP2020138947 A JP 2020138947A JP 2019037114 A JP2019037114 A JP 2019037114A JP 2019037114 A JP2019037114 A JP 2019037114A JP 2020138947 A JP2020138947 A JP 2020138947A
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optically active
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benzazabolol
benzazaborole
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JP7220466B2 (en
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孝義 荒井
Takayoshi Arai
孝義 荒井
哲 鍬野
Satoru Kuwano
哲 鍬野
悠成 保坂
Yusei Hosaka
悠成 保坂
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Chiba University NUC
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Abstract

To provide an optically active benzazaborole derivative that has a function as an asymmetric catalyst.SOLUTION: An optically active benzazaborole derivative is represented by formula (1). It has four basic skeletons derived from cinchona alkaloid (cinchonine, cinchonidine, quinine, quinidine), where R1 is hydrogen, a hydroxy group, or an alkoxy group, R2 is a vinyl group or an alkyl group.SELECTED DRAWING: None

Description

本発明は、光学活性ベンズアザボロール誘導体およびその製造方法に関する。 The present invention relates to an optically active benzazabolol derivative and a method for producing the same.

ベンズオキサボロール誘導体は、糖類等の生体高分子のレセプターや医薬品等に利用されている有用化合物である。そのため、物理、化学、生物を問わず様々な学術分野で研究が推進されている。一方で、その窒素類縁体であるベンズアザボロール誘導体は、構造的特徴から様々な機能が期待されているにも関わらず、その製造方法や機能性分子としての応用に関する報告例は少ない。 The benzoxaborol derivative is a useful compound used as a receptor for biopolymers such as saccharides and pharmaceuticals. Therefore, research is being promoted in various academic fields regardless of physics, chemistry, or biology. On the other hand, the benzazaborol derivative, which is a nitrogen analog, is expected to have various functions due to its structural characteristics, but there are few reports on its production method and its application as a functional molecule.

現在報告されているベンズアザボロール誘導体の限られた応用例として、非特許文献１に記載されている合成レクチンとしての利用、及び非特許文献２に記載されているヨウ化物イオンに対する蛍光レセプターとしての利用が報告されている。一方で、非特許文献３にアザボリンユニットをカルボン酸との水素結合形成に活用したアミド化触媒が記載されている。しかし、簡便な光学活性ベンズアザボロール誘導体の製造法の開発や、不斉触媒としての有機合成化学への応用は未開拓である。 As a limited application example of the benzazaborol derivative currently reported, its use as a synthetic lectin described in Non-Patent Document 1 and as a fluorescent receptor for iodide ion described in Non-Patent Document 2. Has been reported to be used. On the other hand, Non-Patent Document 3 describes an amidation catalyst in which an azaborin unit is used to form a hydrogen bond with a carboxylic acid. However, the development of a simple method for producing an optically active benzazabolol derivative and its application to synthetic organic chemistry as an asymmetric catalyst have not been pioneered.

K. L. Bicker, J. Sun, J. J. Lavigne, P. R. Thompson, ACS Comb. Sci. 2011, 13, 232.K. L. Bicker, J. Sun, J. J. Lavigne, P. R. Thompson, ACS Comb. Sci. 2011, 13, 232. R. Zhang, Y.-D. Zhang, L.-X. Wang, C.-H. Ge, Z.-Y. Ma, J.-P. Miao, X.-D. Zhang, Inorg. Chem. Commun. 2016, 74, 52.R. Zhang, Y.-D. Zhang, L.-X. Wang, C.-H. Ge, Z.-Y. Ma, J.-P. Miao, X.-D. Zhang, Inorg. Chem. Commun. 2016, 74, 52. H. Noda, Y. Asada, M. Shibasaki, N. Kumagai, J. Am. Chem. Soc., 2019, 141, 1546.H. Noda, Y. Asada, M. Shibasaki, N. Kumagai, J. Am. Chem. Soc., 2019, 141, 1546.

本発明は、上記課題を鑑み、光学活性ベンズアザボロール誘導体の簡便な新規合成法の開発を目的とする。更に、合成した光学活性ベンズアザボロール誘導体を不斉触媒として有機合成化学に応用する。新規触媒の開発により、新たな医薬品候補化合物等の合成が可能となる。 In view of the above problems, an object of the present invention is to develop a simple new synthetic method for an optically active benzazabolol derivative. Furthermore, the synthesized optically active benzazabolol derivative is applied to synthetic organic chemistry as an asymmetric catalyst. The development of new catalysts will enable the synthesis of new drug candidate compounds and the like.

本発明者らは、上記課題について鋭意検討を行ったところ、シンコナアルカロイド由来の光学活性アミンと市販の２−ホルミルフェニルボロン酸との還元的アルキル化、及び続く分子内脱水反応によって光学活性ベンズアザボロール誘導体の合成に成功した。更に、得られた化合物を不斉触媒として活用する一例として、環状ジオールの不斉スルホニル化反応による光学活性スルホン酸エステル誘導体の製造にも成功し、本発明を完成させるに至った。 As a result of diligent studies on the above problems, the present inventors conducted reductive alkylation of an optically active amine derived from a cincona alkaloid and commercially available 2-formylphenylboronic acid, followed by an intramolecular dehydration reaction, resulting in optically active benz. We succeeded in synthesizing an azabolol derivative. Furthermore, as an example of utilizing the obtained compound as an asymmetric catalyst, we have succeeded in producing an optically active sulfonic acid ester derivative by an asymmetric sulfonylation reaction of a cyclic diol, and have completed the present invention.

即ち、本発明にて合成された光学活性ベンズアザボロール誘導体は、下記式（１）で示される。
That is, the optically active benzazabolol derivative synthesized in the present invention is represented by the following formula (1).

シンコナアルカロイド（シンコニン、シンコニジン、キニーネ、キニジン）に由来する４種の基本骨格を有し、Ｒ１は、水素、ヒドロキシ基、アルコキシ基（メトキシ基、エトキシ基、プロポキシ基、ブトキシ基、ペンチルオキシ基、ヘキシルオキシ基、ヘプチルオキシ基、オクチルオキシ基、ノニルオキシ基、デシルオキシ基）である。Ｒ2は、ビニル基、アルキル基（エチル基、プロピル基、ブチル基、ペンチル基、ヘキシル基、ヘプチル基、オクチル基、ノニル基、デシル基）である。 It has four basic skeletons derived from cincona alkaloids (cinconin, cinconidine, quinine, quinidine), and R 1 is hydrogen, hydroxy group, alkoxy group (methoxy group, ethoxy group, propoxy group, butoxy group, pentyloxy). Group, hexyloxy group, heptyloxy group, octyloxy group, nonyloxy group, decyloxy group). R 2 is a vinyl group or an alkyl group (ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group).

以上、本発明によると、これまでに合成法の確立されていなかった光学活性ベンズアザボロール誘導体が簡便に合成可能となる。その結果、光学活性ベンズアザボロール誘導体の不斉触媒への応用をはじめとし、物理、化学、生物を問わず様々な学術分野で光学活性ベンズアザボロール誘導体を活用する研究の推進が期待される。用いるシンコナアルカロイドの選択による基本骨格の調整に加え、Ｒ１置換基の変更による電子的、及び立体的効果の調整を行うことで、目的の研究に応じた光学活性ベンズアザボロール誘導体を柔軟に提供することができる。 As described above, according to the present invention, an optically active benzazabolol derivative for which a synthetic method has not been established so far can be easily synthesized. As a result, it is expected to promote research on the utilization of optically active benzazabolol derivatives in various academic fields regardless of physics, chemistry, and biology, including the application of optically active benzazabolol derivatives to asymmetric catalysts. To. In addition to the adjustment of the basic skeleton by selecting the cinchona alkaloids, electronic by changing the R 1 substituents, and by adjusting the stereoscopic effect, the optically active benz aza ball rolls derivatives according to the purpose of study flexible to be used Can be provided to.

以下、本発明の実施形態について化学式を参照しつつ説明する。ただし、本発明は多くの異なる形態で実施することが可能であり、以下に示す実施形態に限定されるものではない。 Hereinafter, embodiments of the present invention will be described with reference to chemical formulas. However, the present invention can be implemented in many different embodiments and is not limited to the embodiments shown below.

本実施形態に係る光学活性ベンズアザボロール誘導体は、上記化学式（１）で示されることを特徴とする。 The optically active benzazabolol derivative according to the present embodiment is characterized by being represented by the above chemical formula (1).

本実施形態に係る光学活性ベンズアザボロール誘導体はシンコナアルカロイド（シンコニン、シンコニジン、キニーネ、キニジン）に由来する４種の基本骨格を有し、Ｒ１は、水素、ヒドロキシ基、アルコキシ基（メトキシ基、エトキシ基、プロポキシ基、ブトキシ基、ペンチルオキシ基、ヘキシルオキシ基、ヘプチルオキシ基、オクチルオキシ基、ノニルオキシ基、デシルオキシ基）である。Ｒ2は、ビニル基、アルキル基（エチル基、プロピル基、ブチル基、ペンチル基、ヘキシル基、ヘプチル基、オクチル基、ノニル基、デシル基）である。 The optically active benzazaborol derivative according to the present embodiment has four basic skeletons derived from cincona alkaloids (cinconin, cinconidine, quinine, quinidine), and R 1 is a hydrogen, a hydroxy group, and an alkoxy group (methoxy). Group, ethoxy group, propoxy group, butoxy group, pentyloxy group, hexyloxy group, heptyloxy group, octyloxy group, nonyloxy group, decyloxy group). R 2 is a vinyl group or an alkyl group (ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group).

本実施形態に係る光学活性ベンズアザボロール誘導体は様々な反応に触媒として用いることができると考えられ、限定されるわけではないが、不斉スルホニル化反応に好適に用いることができる。 It is considered that the optically active benzazabolol derivative according to the present embodiment can be used as a catalyst for various reactions, and can be suitably used for an asymmetric sulfonylation reaction without limitation.

（光学活性ベンズアザボロール誘導体の製造） (Manufacture of optically active benz azabolol derivative)

まず、下記式（２）で示されるシンコナアルカロイドに対し、アゾジカルボン酸ジイソプロピル、トリフェニルホスフィン、ジフェニルリン酸アジドを作用させる。続いて、トリフェニルホスフィン、水を順に加えることにより下記式（３）で示される、水酸基をアミノ基へと変換したシンコナアルカロイド誘導体を得ることができる。
First, diisopropyl azodicarboxylate, triphenylphosphine, and diphenylphosphoryl azide are allowed to act on the syncona alkaloid represented by the following formula (2). Subsequently, by adding triphenylphosphine and water in this order, a syncona alkaloid derivative represented by the following formula (3) in which a hydroxyl group is converted into an amino group can be obtained.

次に、上記式（３）で示されるシンコナアルカロイド誘導体に対し、２−ホルミルフェニルボロン酸を作用させてイミンを形成させる。そこへ水素化ホウ素ナトリウムを加えて還元する。続く後処理により分子内脱水反応が進行し、上記式（１）に示される光学活性ベンズアザボロール誘導体を得ることができる。 Next, 2-formylphenylboronic acid is allowed to act on the syncona alkaloid derivative represented by the above formula (3) to form an imine. Sodium borohydride is added thereto to reduce the amount. By the subsequent post-treatment, the intramolecular dehydration reaction proceeds, and the optically active benzazabolol derivative represented by the above formula (1) can be obtained.

以上、本実施形態により、例えば不斉スルホニル化反応において広範な基質にて高い不斉収率を与える有機ホウ素触媒として機能する光学活性ベンズアザボロール誘導体を提供することができる。 As described above, according to this embodiment, it is possible to provide an optically active benzazabolol derivative that functions as an organoboron catalyst that gives a high asymmetric yield in a wide range of substrates in, for example, an asymmetric sulfonylation reaction.

以下、上記実施形態の光学活性ベンズアザボロール誘導体について実際に作成し、その効果について確認を行った。以下説明する。 Hereinafter, the optically active benzazabolol derivative of the above embodiment was actually prepared, and its effect was confirmed. This will be described below.

本実施例では、下記式（４）で示される光学活性ベンズアザボロール誘導体を作成し、触媒として不斉スルホニル化反応に用いた。
In this example, an optically active benzazabolol derivative represented by the following formula (4) was prepared and used as a catalyst in an asymmetric sulfonylation reaction.

（光学活性ベンズアザボロール誘導体の合成）
下記反応式（５）に従い、上記式（４）の合成を行った。
(Synthesis of optically active benzazabolol derivative)
The above formula (4) was synthesized according to the following reaction formula (5).

まず、上記反応式（５）に従い、シンコニジン（１．４７ｇ、５．０ｍｍｏｌ）、トリフェニルホスフィン（１．９７ｇ、７．５ｍｍｏｌ）を無水ＴＨＦ（２４ｍL）に溶かし、氷浴につけて氷冷する。そこにアゾジカルボン酸ジイソプロピル（１．５０ｍL、７．５ｍｍｏｌ）を加える。続いて、無水ＴＨＦ（１２ｍL）に溶かしたジフェニルリン酸アジド（１．６０ｍL、７．５ｍｍｏｌ）をゆっくりと加え、アルゴン雰囲気下、氷浴を除き、室温で１３時間攪拌する。更に、５０度に昇温して２時間攪拌する。その後、トリフェニルホスフィン（３．２８ｇ、１２．５ｍｍｏｌ）を加え、５０度で２時間攪拌する（注意：発泡）。反応液を室温まで冷やし、蒸留水（１．５ｍL）を加えて室温で２６時間攪拌する。その後、ジクロロメタンを加えて希釈し、ｐHが２になるまで１Nの塩酸水溶液をゆっくりと加える。水相をジクロロメタンで３度洗浄し、続いてアンモニア水を加えてｐHを１０にする。水相にジクロロメタンを加えて３度抽出し、有機相を飽和食塩水で洗浄し、硫酸ナトリウムを用いて乾燥したのち、減圧濃縮する。黄色油状のシンコニジン誘導体を９７％の収率で得た。 First, according to the above reaction formula (5), cinchonidine (1.47 g, 5.0 mmol) and triphenylphosphine (1.97 g, 7.5 mmol) are dissolved in anhydrous THF (24 mL), and the mixture is placed in an ice bath and ice-cooled. Diisopropyl azodicarboxylate (1.50 mL, 7.5 mmol) is added thereto. Subsequently, diphenylphosphoryl azide (1.60 mL, 7.5 mmol) dissolved in anhydrous THF (12 mL) is slowly added, and the mixture is stirred at room temperature for 13 hours under an argon atmosphere, excluding the ice bath. Further, the temperature is raised to 50 degrees and the mixture is stirred for 2 hours. Then, triphenylphosphine (3.28 g, 12.5 mmol) is added, and the mixture is stirred at 50 ° C. for 2 hours (Note: foaming). The reaction mixture is cooled to room temperature, distilled water (1.5 mL) is added, and the mixture is stirred at room temperature for 26 hours. Then, dichloromethane is added to dilute, and 1N aqueous hydrochloric acid solution is slowly added until the pH becomes 2. The aqueous phase is washed 3 times with dichloromethane, followed by the addition of aqueous ammonia to bring the pH to 10. Dichloromethane is added to the aqueous phase and extracted three times, the organic phase is washed with saturated brine, dried over sodium sulfate, and concentrated under reduced pressure. A yellow oily cinchonidine derivative was obtained in 97% yield.

次に、上記で得たシンコニジン誘導体（１．４７ｇ、５．０ｍｍｏｌ）を無水１，２−ジクロロエタン（１５ｍL）に溶かし、２−ホルミルフェニルボロン酸（１．１２ｇ、７．５ｍｍｏｌ）とモレキュラーシーブス４A（４．５ｇ）を加え、アルゴン雰囲気下、室温で２２時間攪拌する。その後、モレキュラーシーブス４Aをろ過し、減圧濃縮する。生じた黄色いアモルファス状のイミンをメタノール（１５ｍL）に溶かし、０度に冷やす。水素化ホウ素ナトリウム（３７８ｍｇ、１０．０ｍｍｏｌ）を少しずつ加える（注意：発泡）。その後、室温まで昇温し、４時間攪拌する。水を加えて反応を停止し、ジクロロメタンを加えて３度抽出する。得られた有機相を硫酸ナトリウムにより乾燥したのち、減圧濃縮する。残渣をアルミナカラムクロマトグラフィー（展開溶媒クロロホルム／メタノール＝１：０から１０：１）により精製し、上記式（４）に示す２−（（Ｓ）−ｑｕｉｎｏｌｉｎ−４−ｙｌ（（１Ｓ，２Ｓ，４Ｓ，５Ｒ）−５−ｖｉｎｙｌｑｕｉｎｕｃｌｉｄｉｎ−２−ｙｌ）ｍｅｔｈｙｌ）−２，３−ｄｉｈｙｄｒｏ−１Ｈ−ｂｅｎｚｏ［ｃ］［１，２］ａｚａｂｏｒｏｌ−１−ｏｌ（Ａ）の白色固体を７２％の収率で得た。
（Ａ）の機器データ：
１Ｈ ＮＭＲ （４００ ＭＨｚ， ＣＤ３ＯＤ）： δ ８．９４ （ｄ， Ｊ ＝ ４．５ Ｈｚ， １Ｈ）， ８．４４ （ｄ， Ｊ ＝ ７．７ Ｈｚ， １Ｈ）， ８．１０ （ｄ， Ｊ ＝ ８．４ Ｈｚ， １Ｈ）， ７．８６−７．７１ （ｍ， ３Ｈ）， ７．４９ （ｄ， Ｊ ＝ ６．６ Ｈｚ， １Ｈ）， ７．２０−６．９６ （ｍ， ２Ｈ）， ６．８６ （ｂｒ ｓ， １Ｈ）， ６．００−５．７６ （ｍ， １Ｈ）， ５．２７−４．９５ （ｍ， ３Ｈ）， ３．８８ （ｂｒ， ２Ｈ）， ３．５９−３．２１ （ｍ， ３Ｈ）， ３．０５−２．６７ （ｍ， ２Ｈ）， ２．３６ （ｂｒ ｓ， １Ｈ）， １．６２ （ｂｒ ｓ， ３Ｈ）， １．４０−１．２８ （ｍ， １Ｈ）， ０．７３ （ｂｒ ｓ， １Ｈ）； １３Ｃ ＮＭＲ （１００ ＭＨｚ， ＣＤ３ＯＤ）： δ １５０．８， １４９．１， １４４．９， １４２．６， １３４．１， １３１．２， １３０．２， １２９．６， １２８．６， １２８．３， １２７．９， １２４．８， １２１．６， １１５．０， ６１．３， ５６．６， ５２．２， ４１．９， ４０．８， ２８．７， ２８．４， ２６．６； ＩＲ （ｎｅａｔ） ３２５５， ３０６０， ３００１， ２９４１， １５９３， １４４６， １３９２， １３６０， １２１８， ７４５ ｃｍ−１； ＨＲＭＳ （ＥＳＩ＋） ｃａｌｃｄ ｆｏｒ Ｃ２６Ｈ２９ＢＮ３Ｏ ［Ｍ ＋ Ｈ］＋ ４１０．２４０４： ｆｏｕｎｄ ４１０．２３９４； ［α］Ｄ ２４ ＝ ＋３６．８ （ｃ ＝ １．０， ＣＨＣｌ３）． Next, the cinchonidine derivative (1.47 g, 5.0 mmol) obtained above was dissolved in anhydrous 1,2-dichloroethane (15 mL), and 2-formylphenylboronic acid (1.12 g, 7.5 mmol) and molecular sieves 4A were dissolved. (4.5 g) is added, and the mixture is stirred at room temperature for 22 hours under an argon atmosphere. Then, Molecular Sieves 4A is filtered and concentrated under reduced pressure. The resulting yellow amorphous imine is dissolved in methanol (15 mL) and cooled to 0 ° C. Sodium borohydride (378 mg, 10.0 mmol) is added in small portions (Note: foaming). Then, the temperature is raised to room temperature and the mixture is stirred for 4 hours. Water is added to stop the reaction, dichloromethane is added and the mixture is extracted three times. The obtained organic phase is dried over sodium sulfate and then concentrated under reduced pressure. The residue was purified by alumina column chromatography (developing solvent chloroform / methanol = 1: 0 to 10: 1) and represented by the above formula (4) in 2-((S) -quinolin-4-yl ((1S, 2S,). 4S, 5R) -5-vinylquinuclidein-2-yl) methanol) -2,3-dihydro-1H-benzo [c] [1,2] A white solid of azaborol-1-ol (A) in a yield of 72%. I got it in.
Equipment data of (A):
1 1 H NMR (400 MHz, CD 3 OD): δ 8.94 (d, J = 4.5 Hz, 1H), 8.44 (d, J = 7.7 Hz, 1H), 8.10 (d) , J = 8.4 Hz, 1H), 7.86-7.71 (m, 3H), 7.49 (d, J = 6.6 Hz, 1H), 7.20-6.96 (m, 2H), 6.86 (br s, 1H), 6.00-5.76 (m, 1H), 5.27-4.95 (m, 3H), 3.88 (br, 2H), 3. 59-3.21 (m, 3H), 3.05-2.67 (m, 2H), 2.36 (br s, 1H), 1.62 (br s, 3H), 1.40-1. 28 (m, 1H), 0.73 (br s, 1H); 13 C NMR (100 MHz, CD 3 OD): δ 150.8, 149.1, 144.9, 142.6, 134.1, 131.2, 130.2, 129.6, 128.6, 128.3, 127.9, 124.8, 121.6, 115.0, 61.3, 56.6, 52.2, 41. 9, 40.8, 28.7, 28.4, 26.6; IR (neat) 3255, 3060, 3001, 2941, 1593, 1446, 1392, 1360, 1218, 745 cm -1 ; HRMS (ESI +) calcd for C 26 H 29 BN 3 O [M + H] + 410.2404: found 410.2394; [α] D 24 = +36.8 (c = 1.0, CHCl 3 ).

（光学活性スルホン酸エステルの合成）
次に、この得られた光学活性ベンズアザボロール誘導体（４）８．２ｍｇを触媒として活用し、ｃｉｓ−１，２−シクロヘキサンジオールと塩化スルホニルの不斉スルホニル化反応を行った。その結果を下記反応式（６）に示しておく。 (Synthesis of optically active sulfonic acid ester)
Next, 8.2 mg of the obtained optically active benzazabolol derivative (4) was used as a catalyst to carry out an asymmetric sulfonylation reaction of cis-1,2-cyclohexanediol and sulfonyl chloride. The result is shown in the following reaction formula (6).

上記の触媒及びｃｉｓ−１，２−シクロヘキサンジオール（２３．２ｍｇ、０．２ｍｍｏｌ）、炭酸ナトリウム（４２．４ｍｇ、０．４ｍｍｏｌ）、ｐ−トルエンスルホン酸塩化物（７６．３ｍｇ、０．４ｍｍｏｌ）を反応容器に加え、１−メチルイミダゾールの１０ｍＭアセトニトリル溶液１ｍLに溶かし、アルゴン雰囲気下、室温で１３時間攪拌した。その結果、反応が９２％進行し、スルホン酸エステルのエナンチオ選択性が８１％であった。この結果より、本発明により得られた光学活性ベンズアザボロール誘導体の触媒としての有用性を確認することができた。また、ベンゼンスルホン酸塩化物を基質に用いて反応を行った場合、反応は９６％進行し、目的物は８３％ｅｅであった。更に４−クロロベンゼンスルホン酸塩化物を基質に用いて反応を行った場合、反応は９０％進行し、目的物は８０％ｅｅであった。
The above catalyst and cis-1,2-cyclohexanediol (23.2 mg, 0.2 mmol), sodium carbonate (42.4 mg, 0.4 mmol), p-toluenesulfonated product (76.3 mg, 0.4 mmol). Was added to the reaction vessel, dissolved in 1 mL of a 10 mM acetonitrile solution of 1-methylimidazole, and stirred at room temperature for 13 hours under an argon atmosphere. As a result, the reaction proceeded by 92%, and the enantioselectivity of the sulfonic acid ester was 81%. From this result, it was confirmed that the optically active benzazaborol derivative obtained by the present invention is useful as a catalyst. When the reaction was carried out using a benzenesulfonated product as a substrate, the reaction proceeded by 96% and the target product was 83% ee. Further, when the reaction was carried out using 4-chlorobenzene sulfonate as a substrate, the reaction proceeded by 90% and the target product was 80% ee.

以上本実施例により本触媒の効果を確認することができ、広範な基質において高い不斉収率を与える触媒を提供することができるのを確認した。 As described above, it was confirmed that the effect of this catalyst can be confirmed by this example, and that a catalyst that gives a high asymmetric yield in a wide range of substrates can be provided.

本発明で開発した光学活性ベンズアザボロール誘導体は、新たな有機ホウ素触媒として産業上の利用可能性がある。 The optically active benzazabolol derivative developed in the present invention has industrial applicability as a new organoboron catalyst.

Claims (1)

下記式（１）で示される光学活性ベンズアザボロール誘導体。
シンコナアルカロイド（シンコニン、シンコニジン、キニーネ、キニジン）に由来する４種の基本骨格を有し、Ｒ１は、水素、ヒドロキシ基、アルコキシ基（メトキシ基、エトキシ基、プロポキシ基、ブトキシ基、ペンチルオキシ基、ヘキシルオキシ基、ヘプチルオキシ基、オクチルオキシ基、ノニルオキシ基、デシルオキシ基）である。Ｒ2は、ビニル基、アルキル基（エチル基、プロピル基、ブチル基、ペンチル基、ヘキシル基、ヘプチル基、オクチル基、ノニル基、デシル基）である。 An optically active benzazabolol derivative represented by the following formula (1).
It has four basic skeletons derived from cincona alkaloids (cinconin, cinconidine, quinine, quinidine), and R 1 is hydrogen, hydroxy group, alkoxy group (methoxy group, ethoxy group, propoxy group, butoxy group, pentyloxy). Group, hexyloxy group, heptyloxy group, octyloxy group, nonyloxy group, decyloxy group). R 2 is a vinyl group or an alkyl group (ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group).
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JP2015145344A (en) * 2014-02-03 2015-08-13 国立大学法人 名古屋工業大学 PRODUCTION METHOD OF α,β-DIAMINO ACID HAVING OPTICALLY ACTIVE ASYMMETRIC TETRASUBSTITUTED CARBON
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