論文 2018


Chiral Pyrophosphoric Acid Catalysts for the para-Selective and Eanantioselective Aza-Friedel–Crafts Reaction of Phenols

Haruka Okamoto, Kohei Toh, Takuya Mochizuki, Hidefumi Nakatsuji, Akira Sakakura* , Manabu Hatano*, Kazuaki Ishihara*

The article was first published on 22 August 2018
Synthesis 2018, 50(xx), xxxx-xxxx.

DOI: 10.1055/s-0037-1610250

Chiral BINOL-derived pyrophosphoric acid catalysts were developed and used for the regio- and enantioselective aza-Friedel–Crafts reaction of phenols with aldimines. ortho/para-Directing phenols could react at the para-position selectively with moderate to good enantioselectivities. Moreover, the gram-scale transformation of a product into the key intermediate for the antifungal agent (R)-bifonazole was demonstrated.

[北大 松永研との共同研究成果]
"Pentamethylcyclopentadienyl rhodium(III)–chiral disulfonate hybrid catalysis for enantioselective C–H bond functionalization"
Shun Satake, Takumaru Kurihara, Keisuke Nishikawa, Takuya Mochizuki, Manabu Hatano, Kazuaki Ishihara, Tatsuhiko Yoshino* & Shigeki Matsunaga*
Nat. Catal. 2018, 1(8), 585–591.  Published: 23 July 2018
DOI: 10.1038/s41929-018-0106-5
https://www.nature.com/articles/s41929-018-0106-5

プレスリリース

http://www.nagoya-u.ac.jp/.../upload.../20180724_engg_1.pdf

日刊工業新聞(2018年8月2日25面)

見出し「1工程で鏡像異性体合成 北大など」

https://www.nikkan.co.jp/articles/view/00483484?isReadConfirmed=true

国立環境研究所ニュース(2018年7月24日)

見出し「北大と名大、医薬品合成における環境負荷低減に役立つハイブリッド触媒の作製に成功」

http://tenbou.nies.go.jp/news/jnews/detail.php?i=24703

Press Release (August 9, 2018)

Hybrid catalyst with high enantiomer selectivity

http://en.nagoya-u.ac.jp/research/activities/news/2018/08/hybrid-catalyst-with-high-enantiomer-selectivity.html

 

ホウ素触媒でカルボン酸を自在に変換する! アシロキシボラン中間体を鍵とするエナンチオ選択的変換反応
堀部貴大、石原一彰
化学 2018, 73(8), 25–28.

私の自慢「根拠のないプライドを支えに、アカデミアの世界へ ポスドクでやり残したもの」
石原一彰
化学と工業 2018, 71(7), 598–601.
http://www.chemistry.or.jp/journal/ci1807.pdf

Enantioselective Aza-Friedel–Crafts Reaction of Furan with α-Ketimino Esters Induced by a Conjugated Double Hydrogen Bond Network of Chiral Bis(phosphoric Acid) Catalysts

Manabu Hatano, Haruka Okamoto, Taro Kawakami, Kohei Toh, Hidefumi Nakatsuji, Akira Sakakura* and Kazuaki Ishihara*

The article was first published on 25 Jun 2018
Chem. Sci. 2018, 9(30), 6361-6367.
DOI: 10.1039/C8SC02290A

Chiral C2- and C1-symmetric BINOL-derived bis(phosphoric acid) catalysts, which have OP(=O)(OH)2/OP(=O)(OH)(OR) moieties at the 2,2’-positions, were developed and used for the enantioselective aza-Friedel–Crafts reaction of 2-methoxyfuran with α-ketimino esters for the first time. The intramolecular conjugated double hydrogen bond network is a key to increasing the Brønsted acidity and preventing deactivation of the catalysts. Highly functionalized α-amino acid derivatives with a chiral quaternary carbon center could be transformed into versatile optically active N- and O-heterocycles and an α-aryl-substituted serine.

 

Selected as a Back Cover Picture
Chem. Sci. 2018, 9(30), 6453-6454.
DOI: 10.1039/C8SC90158A

Asymmetric Total Synthesis of (−)-Maldoxin, a Common Biosynthetic Ancestor of the Chloropupukeananin Family

Takahiro Suzuki,* Soichiro Watanabe, Muhammet Uyanik, Kazuaki Ishihara, Susumu Kobayashi, and Keiji Tanino*
Org. Lett. 2018, 20(13), 3919–3922.
Publication Date (Web): June 8, 2018 (Letter)
DOI: 10.1021/acs.orglett.8b01502

Thiourea–I2 as Lewis Base–Lewis Acid Cooperative Catalysts for Iodochlorination of Alkene with In Situ-Generated I–Cl
Takahiro Horibe , Yasutaka Tsuji, and Kazuaki Ishihara*
ACS Catal. 2018, 8(7), 63626366
DOI: 10.1021/acscatal.8b01565
Publication Date (Web): June 7, 2018
https://pubs.acs.org/doi/10.1021/acscatal.8b01565

▼巻頭言「有機反応を意のままに操るために」

石原一彰

有機合成化学協会誌 2018, 76(6), 563.

オープンアクセス

▼Enantioselective Halo-oxy- and Halo-azacyclizations Induced by Chiral Amidophosphate Catalysts and Halo-Lewis Acids
Yanhui Lu, Hidefumi Nakatsuji, Yukimasa Okumura, Lu Yao, and Kazuaki Ishihara*
J. Am. Chem. Soc. 2018, 140(19), 6039-6043.
DOI: 10.1021/jacs.8b02607
Publication Date (Web): April 30, 2018
https://pubs.acs.org/doi/pdf/10.1021/jacs.8b02607

ortho-Substituent Effect on 2,4-Bis(trifluoromethyl)phenylboronic Acid-Catalyzed Dehydrative Condensation between Carboxylic Acids and Amines
Ke Wang, Yanhui Lu and Kazuaki Ishihara*
Chem. Commun. 2018, 54(43), 5410–5413. (Inside Cover Picture)

The article was first published on 24 Apr 2018

DOI: 10.1039/C8CC02558D

Boron Tribromide‐Assisted Chiral Phosphoric Acid Catalysts for Enantioselective [2+2] Cycloaddition

Tatsuhiro Sakamoto, Takuya Mochizuki, Yuta Goto, Manabu Hatano,* Kazuaki Ishihara*
Chem. Asian J. 2018, 13(17), 2373–2377.

First published: 30 March 2018
https://doi.org/10.1002/asia.201800351

DOI: 10.1002/asia.201800351

Proton challenge: BBr3‐assisted chiral phosphoric acid catalysts were used for the enantioselective [2+2] cycloaddition of vinyl sulfides with acroleins. One of the obtained [2+2] cycloadducts could be readily transformed to a key intermediate for (+)‐frontalin as a pheromone of Asian elephants.

Metal-Free Transesterification Catalyzed by Tetramethylammonium Methyl Carbonate

Manabu Hatano, Yuji Tabata, Yurika Yoshida, Kohei Toh, Kenji Yamashita, Yoshihiro Ogura, and  Kazuaki Ishihara*

Green Chem. 2018, 20(6), 1193–1198.

The article was received on 26 Dec 2017, accepted on 13 Feb 2018 and first published on 13 Feb 2018.

Environmentally benign metal-free tetramethylammonium methyl carbonate is effective as a catalyst for the chemoselective, scalable, and reusable transesterification of various esters and alcohols in common organic solvents. In situ-generated highly active species, tetramethylammonium alkoxides, can greatly avoid the self-decomposition at ≤110 °C, and reusable. In particular, chelating substrates, such as amino alcohols, diols, triols, sugar derivatives, alkaloids, α-amino acid esters, etc., which deactivate conventional metal salt catalysts, can be used. A 100 gram scale biodiesel production was also demonstrated.

Enantioselective Aza-Friedel-Crafts Reaction of Indoles with Ketimines Catalyzed by Chiral Potassium Binaphthyldisulfonates

Manabu Hatano, Takuya Mochizuki, Keisuke Nishikawa, Kazuaki Ishihara*
ACS Catal. 2018, 8, 349–353.
Publication Date (Web): December 4, 2017 (Letter)

The enantioselective aza-Friedel–Crafts reaction of indoles with low-reactive ketimines has been developed in the presence of a chiral monopotassium binaphthyldisulfonate as a strong Brønsted acid catalyst. A broad substrate scope was achieved, and the corresponding 3-indolylmethanamines with a chiral quaternary carbon center were obtained in high yields with high enantioselectivities. The addition of a catalytic amount of acetic acid considerably promoted the reaction, and a gram-scale reaction could be achieved with reduced catalyst loading.

Recruit

ポスドク及び大学院生を募集中です。

当研究室では学部生、大学院生の研究室見学を随時受け付けております。

希望者は、石原教授までメールでお問い合わせ下さい。

 

Postdoctoral and graduate students is being recruited.In our laboratory will be accepted at any time undergraduate, graduate student visits to laboratories.Those who wish, please contact us by e-mail to Professor Ishihara.

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ISHIHARA GROUP

名古屋大学

大学院工学研究科 有機・高分子化学専攻(工学部 化学生命工学科)
有機化学講座

触媒有機合成学研究グループ

〒464-8603 名古屋市千種区不老町

B2-3(611)

 

Laboratory of Catalysis in Organic Synthesis, Research Group of Molecular Chemistry, Graduate Department of Molecular and Macromolecular Chemistry, Graduate School of Engineering (Undergraduate Department of Chemistry and Biotechnology, School of Engineering), Nagoya University

B2-3(611), Furo-cho, Chikusa, Nagoya 464-8603, Japan