Synthesis of Enantiomerically Pure Oxa[9]helicene Derivatives by a Nucleophilic Cyclodehydration Reaction of Helical 1,1′-Bibenzo[c]phenanthrenylidene-2,2′-dione

Abstract

Enantiomerically pure 9-substituted 11-oxa[9]helicene derivatives have been synthesized through furan-ring formation by a nucleophilic cyclodehydration reaction of enantiomerically pure helical polycondensed 2,2′-diphenoquinone derivatives (1,1′-bibenzo[c]phenanthrenylidene-2,2′-diones). (P)-2,2′-diphenoquinone derivatives afforded (P)-oxa[9]helicenes, whereas (M)-2,2′-diphenoquinone derivatives afforded the corresponding (M)-oxa[9]helicenes. Therefore, the ring-closing reaction afforded the corresponding enantiomerically pure products without decreasing the enantiomeric excess, and it proceeded stereospecifically with retention of the configuration. The thermal stability of an oxa[9]helicene was studied by determining the decrease in its enantiomeric excess at various temperatures, and its racemization barrier was found to be 165.6 kJ/mol.

Key words

helical structures - oxahelicenes - O-heterocycles - racemization - cyclodehydration - asymmetric synthesis

Publication History

Received: 17 October 2021

Accepted after revision: 02 November 2021

Accepted Manuscript online:
02 November 2021

Article published online:
24 November 2021

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• 12 Oxahelicenes 2a and 3a; General Procedure A round-bottomed flask was charged with the appropriate (P)- or (M)-1 (29.04 mg, 0.06 mmol), Lawesson’s reagent (2 equiv), and toluene (4 mL), and the mixture was stirred at 60 °C for 16–20 h until the reaction was complete. The solvent was evaporated, and the mixture was passed through a silica gel column with CHCl₃ as eluent. The first yellow-colored fraction was evaporated to give the required product. (P)-Oxa[9]helicene (2a) White solid; yield: 87%; mp >300 ℃; [α]_D ²⁵ +2087 (c 1.13 × 10^–2, MeCN). IR (KBr): 3040 (arom C–H), 1250 (–O–), 830, 730 cm^–1. ¹H NMR (500 MHz, CDCl₃): δ = 5.72 (t, J = 7.5 Hz, 2 H), 6.19 (d, J = 8.5 Hz, 2 H), 6.76 (t, J = 7.3 Hz, 2 H), 7.31 (d, J = 8.0 Hz, 2 H), 7.37 (d, J = 8.5 Hz, 2 H), 7.57 (d, J = 8.5 Hz, 2 H), 7.60 (d, J = 8.5 Hz, 2 H), 8.11 (d, J = 8.5 Hz, 2 H), 8.27 (d, J = 8.5 Hz, 2 H), 8.31 (d, J = 8.0 Hz, 2 H). ¹³C NMR (100 MHz, CDCl₃): δ = 110.95, 121.02, 122.19, 124.03, 124.33, 124.62, 125.15, 125.34, 126.20, 126.27, 126.50, 126.93, 127.29, 127.61, 129.45, 129.51, 129.94, 154.22. HRMS (EI): m/z [M]⁺ calcd for C₃₆H₂₀O: 468.1514; found: 468.1518.