Synthesis
DOI: 10.1055/s-0037-1610250
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© Georg Thieme Verlag Stuttgart · New York

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

Haruka Okamoto
a  Graduate School of Engineering, Nagoya University, Furo-cho, Chikusa, Nagoya 464-8603, Japan   Email: hatano@chembio.nagoya-u.ac.jp   Email: ishihara@cc.nagoya-u.ac.jp
,
Kohei Toh
a  Graduate School of Engineering, Nagoya University, Furo-cho, Chikusa, Nagoya 464-8603, Japan   Email: hatano@chembio.nagoya-u.ac.jp   Email: ishihara@cc.nagoya-u.ac.jp
,
Takuya Mochizuki
a  Graduate School of Engineering, Nagoya University, Furo-cho, Chikusa, Nagoya 464-8603, Japan   Email: hatano@chembio.nagoya-u.ac.jp   Email: ishihara@cc.nagoya-u.ac.jp
,
Hidefumi Nakatsuji
a  Graduate School of Engineering, Nagoya University, Furo-cho, Chikusa, Nagoya 464-8603, Japan   Email: hatano@chembio.nagoya-u.ac.jp   Email: ishihara@cc.nagoya-u.ac.jp
,
b  Graduate School of Natural Science and Technology, Okayama University, 3-1-1 Tsushimanaka, Kita-ku, Okayama 700-8530, Japan   Email: sakakura@okayama-u.ac.jp
,
a  Graduate School of Engineering, Nagoya University, Furo-cho, Chikusa, Nagoya 464-8603, Japan   Email: hatano@chembio.nagoya-u.ac.jp   Email: ishihara@cc.nagoya-u.ac.jp
,
a  Graduate School of Engineering, Nagoya University, Furo-cho, Chikusa, Nagoya 464-8603, Japan   Email: hatano@chembio.nagoya-u.ac.jp   Email: ishihara@cc.nagoya-u.ac.jp
› Author Affiliations
This work was financially supported by JSPS KAKENHI Grant Numbers JP26288046, JP17H03054, and JP15H05810 in Precisely Designed Catalysts with Customized Scaffolding.
Further Information

Publication History

Received: 27 June 2018

Accepted after revision: 24 July 2018

Publication Date:
22 August 2018 (eFirst)

Abstract

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.

Supporting Information

 
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  • 23 We performed the 31P NMR (CDCl3) analysis after the routine workup with Et3N. As a result, (R)-3·(Et3N)n was observed as a sole peak at –19.7 ppm, which strongly suggests that (R)-3a was intact during the reaction [cf. 31P NMR (CDCl3) spectra; (R)-3a: δ = –20.8; (R)-2a: δ = –0.4].
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  • 25 As shown in Table 2 and Scheme 3, the catalytic activity of (R)-1a was lower than that of (R)-3a, and (R)-1a did not promote the reactions of 5b (0.01 M CHCl3) effectively at 0 °C for 3 h. A mixture of the corresponding adducts 6 and 7 was obtained in <5% yield.

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