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

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.

Key words

Brønsted acid - phosphoric acid - pyrophosphoric acid - organocatalyst - aza-Friedel–Crafts reaction - phenol - regio-selectivity

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Selected papers for ortho-selective catalytic asymmetric FC reaction of phenols with α,β-unsaturated carbonyl compounds, nitro olefins, α-keto esters, aldimines, isatins, CF₃-ketimines, etc.
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Only few para-selective catalytic asymmetric FC reaction of phenols has been reported:
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See also see a review:
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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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