Synthesis 2018; 50(23): 4577-4590
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 Enantioselective 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
› Institutsangaben
This work was financially supported by JSPS KAKENHI Grant Numbers JP26288046, JP17H03054, and JP15H05810 in Precisely Designed Catalysts with Customized Scaffolding.
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Publikationsverlauf

Received: 27. Juni 2018

Accepted after revision: 24. Juli 2018

Publikationsdatum:
22. August 2018 (online)


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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  • 14 Very recently, Shao reported a catalytic enantioselective aza-FC reaction of phenols with aldimines with the use of chiral phosphoric acid catalysts. ortho-Adducts were selectively obtained with high enantioselectivities. See ref. 10n.
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  • 19 Unfortunately, we have not yet been able to synthesize chiral bis(phosphoric acid)s and thus the corresponding chiral pyrophosphoric acids with more bulky substituents (e.g., 2,4,6-i-Pr3C6H2) due to the steric constraints. With this regard, we have already discussed the synthetic difficulty of the bulky catalysts in our previous manuscript (ref. 7b).
  • 20 A higher concentration (i.e., >0.1 M based on 5 in CHCl3) gave much lower enantioselectivities, whereas a lower concentration gave almost the same enantioselectivity as with the optimal concentration (0.01 M). Moreover, the effect of the reaction temperature (–40, –20, 0, and 25 °C) was also investigated. As a result, 0 °C gave better results in terms of yield and enantioselectivity than the other temperatures.
  • 21 CHCl3 provided a better yield and enantioselectivity than other low-polarity solvents, such as CH2Cl2, 1,2-dichloroethane, toluene, and benzotrifluoride. In contrast, no reaction occurred when polar solvents were used, such as Et2O, THF, propionitrile, and nitroethane.
  • 22 Aldimines with other N-protecting groups, such as CO2t-Bu (Boc), showed lower enantioselectivities (see Scheme 8). Relatively stable N-CO2CH2Ph (Cbz) aldimines could be used, but showed slightly lower yields with almost the same enantioselectivities as less stable NCO2Me aldimines. Moreover, no reaction occurred when NCO2CH2 (9-fluorenyl) (Fmoc), NSO2Ph, NPh, and NBn aldimines were used.
  • 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].
  • 24 Compounds 6b, 6c, and 6d were subjected to X-ray analysis. See the Supporting Information for details.
  • 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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