Reactions of naphthalene and anthracene derivatives with trifluoromethyl hypofluorite

Abstract

Spiro oxazolidine steroidal nitroxides1 are widely used as spin labels in biological membranes.2-4 In spite of its interest for orientation studies, the configuration of the spiro ring system has never been established. There are

Intermediates in the cleavage of endoperoxides

“…Pale yellow solid; m.p. 282 °C (Lit . 282–284 °C); R f = 0.27 (CHCl 3 /PE 1:1); 1 H NMR (300 MHz, CDCl 3 ): δ = 7.51–7.54 (m, 4H; 2‐H, 3‐H, 6‐H, 7‐H), 7.93–7.96 ppm (m, 4H; 1‐H, 4‐H, 5‐H, 8‐H); 13 C NMR (75 MHz, CDCl 3 ): 121.7 (d; C‐1, C‐4, C‐5, C‐8), 124.1 (s; C‐4a, C‐8a, C‐9a, C‐10a), 126.4 (d; C‐2, C‐3, C‐6, C‐7), 150.0 ppm (s; C‐9, C‐10); IR (KBr): ṽ = 3437 (w), 3074 (w), 1674 (s), 1582 (m), 1327 (m), 1281 (s), 1170 cm −1 (m); HRMS (GC‐TOF): m/z calcd.…”

“…282°C (Lit. [17] Cleavage of endoperoxide 2a under anaerobic conditions. As described in literature, [14] the reaction was performed in a glove box.…”

Enzymatic Cleavage of Aryl Acetates

“…M.p. 282 °C (Lit . 282–284 °C); R f =0.27 (CHCl 3 /PE 1:1); 1 H NMR (300 MHz, CDCl 3 ): δ =7.51–7.54 (m, 4 H; 2‐H, 3‐H, 6‐H, 7‐H), 7.93–7.96 ppm (m, 4 H; 1‐H, 4‐H, 5‐H, 8‐H); 13 C NMR (75 MHz, CDCl 3 ): 121.7 (d, C‐1, C‐4, C‐5, C‐8), 124.1 (s, C‐4a, C‐8a, C‐9a, C‐10a), 126.4 (d, C‐2, C‐3, C‐6, C‐7), 150.0 ppm (s, C‐9, C‐10); HRMS (GC–TOF): m / z calcd for C 14 H 8 O 2 : 208.0524 [ M + ]; found: 208.0528.…”

Dearomatization of α-Unsubstituted β-Naphthols

“…In 1974, Patrick investigated the reaction of CF 3 OF with several naphthalene and anthracene derivatives. 26 Among them, the reaction of CF 3 OF with β-naphthol generated l, l-difluoro-2-naphthone, realizing the dearomatization of β-naphthol (Scheme 17 ). The reaction of CF 3 OF with β-naphthol to form l, l-difluoro-2-naphthone achieved the dearomatization of β-naphthol.…”