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Synlett 2024; 35(08): 925-929
DOI: 10.1055/a-2202-4667
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Special Issue dedicated to Keith Fagnou

Synthesis of Axially Chiral Bibenzo[g]coumarin Derivatives by Rhodium-Catalyzed Oxidative Annulation of Thiocarbamates

Ryo Takishima
a   Department of Applied Chemistry, Graduate School of Engineering, Osaka University, Suita, Osaka 565-0871, Japan
,
Koushik Ghosh
a   Department of Applied Chemistry, Graduate School of Engineering, Osaka University, Suita, Osaka 565-0871, Japan
,
Yuji Nishii  ∗
a   Department of Applied Chemistry, Graduate School of Engineering, Osaka University, Suita, Osaka 565-0871, Japan
b   Center for Future Innovation, Graduate School of Engineering, Osaka University, Suita, Osaka 565-0871, Japan
,
Masahiro Miura  ∗
c   Innovative Catalysis Science Division, Institute for Open and Transitionary Research Initiatives (ICS-OTRI), Osaka University, Suita, Osaka 565-0871, Japan
› InstitutsangabenThis research was supported by a Grant-in-Aid for Scientific Research from JSPS (Specially Promoted Research, Grant No. JP 17H06092).
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Abstract

Polyaromatic organic compounds have attracted significant attention because of their wide range of applications in various functional materials. Recently, transition-metal-catalyzed C–H bond activation and the subsequent oxidative cyclization with unsaturated compounds has emerged as a promising synthetic method for multiring systems. We report a two-step synthesis of binaphthyl-fused chiral bibenzo[g]coumarin derivatives by Rh-catalyzed annulative coupling reaction of BINOL-based thiocarbamates with alkynes. The optical properties of the coupling products were evaluated.

Key words

coumarins - rhodium catalysis - C–H bond activation - BINOLs - circular dichroism - polycyclic heteroaromatic compounds

Supporting Information

    Supporting information for this article is available online at https://doi.org/10.1055/a-2202-4667.
  • Supporting Information


Publikationsverlauf

Eingereicht: 28. August 2023

Angenommen nach Revision: 01. November 2023

Accepted Manuscript online:
01. November 2023

Artikel online veröffentlicht:
14. Dezember 2023

© 2023. Thieme. All rights reserved

Georg Thieme Verlag KG
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  • References and Notes

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  • 13 O,O′-1,1′-Binaphthalene-2,2′-diyl Bis[diethyl(thiocarbamate)] (1) A 20 mL two-necked round-bottomed flask equipped with a N2 balloon was charged with (S)- or (R)-BINOL (286 mg, 1.0 mmol), DABCO (224 mg, 2.0 mmol), and THF (3.0 mL). A 60% paraffin dispersion of NaH (120 mg, 3.0 mmol) was added in a portionwise manner, then diethylthiocarbamoyl chloride (334 mg, 2.2 mmol) was added dropwise from a syringe. The resulting mixture was stirred in an oil bath at 60 °C for 18 h, then poured into ice–water and extracted with CHCl3 (×3). The combined organic layer was washed with brine, dried (Na2SO4), and concentrated in vacuo. The residue was purified by column chromatography [silica gel, hexane–EtOAc (5:1)] to give a white solid; yield: (R)-1: 442 mg (86%); (S)-1: 429 mg (83%); mp 106–108 °C. HPLC [CHIRAL ART Amylose-SA column, hexane–CH3Cl (90:10), 0.5 mL/min, 25 °C, λ = 250.0 nm]: (R)-1: t R = 29.66 min; (S)-1: t R = 43.35 min. 1H NMR (400 MHz, CDCl3): δ = 7.94 (d, J = 8.84 Hz, 2 H), 7.87 (d, J = 8.16 Hz, 2 H), 7.57 (d, J = 8.92 Hz, 2 H), 7.51 (d, J = 8.44 Hz, 2 H), 7.43 (td, J = 7.5, 1.16, 2 H), 7.29 (td, J = 7.5, 1.18, 2 H), 3.65–3.40 (m, 4 H), 3.11–2.80 (m, 4 H), 0.89 (t, J = 7.08 Hz, 6 H), 0.57 (t, J = 7.08 Hz, 6 H). 13C NMR (100 MHz, CDCl3): δ = 185.15, 149.48, 133.36, 131.50, 128.21, 127.62, 126.97, 126.32, 125.68, 124.09, 123.73, 47.44, 43.40, 12.65, 11.26. HRMS (APCI): m/z [M + H]+ calcd for C30H33N2O2S2: 517.1977; found: 517.1948. Bibenzo[g]chromenediones 3a–g; General Procedure An oven-dried 10 mL screw-top tube was charged with (R)-1 (51.7 mg, 0.1 mmol), the appropriate alkyne 2 (0.25 mmol), [Cp*RhCl2]2 (6.2 mg, 0.01 mmol), AgSbF6 (13.7 mg, 0.04 mmol), Cu(OAc)2·H2O (44.0 mg, 0.22 mmol), and CuOAc (24.5 mg, 0.20 mmol). The tube was then filled with N2, and diglyme (2.0 mL) and 1,4-dioxane (2.0 mL) were added from a syringe. The mixture was then heated at 140 °C in an oil bath for 18 h. The resulting mixture was filtered through a pad of Celite, eluting with EtOAc, and the filtrate was concentrated in vacuo. The residue was purified by column chromatography [silica gel, hexane–EtOAc (4:1)] and GPC (CHCl3). The corresponding (S)-isomers were synthesized similarly in small batches for analysis. (R)-3,3′,4,4′-Tetraphenyl-2H,2′H-[10,10′-bibenzo[g]chromene]-2,2′-dione [(R)-3a] White solid; yield: 38 mg (55%); mp >300 °C; [α]D 20 +92.9 [(S)-3a], –94.4 [(R)-3a] (c = 0.1, CHCl3). HPLC [CHIRAL ART Amylose-SA column, hexane–CH3Cl (70:30), 0.2 mL/min, 25 °C, λ = 250.0 nm]: (S)-3a: t R = 27.17 min; (R)-3a: t R = 23.14 min. 1H NMR (400 MHz, CDCl3): δ = 7.14–7.20 (m, 10 H), 7.22–7.24 (m, 2 H), 7.28–7.30 (m, 2 H), 7.35–7.46 (m, 12 H), 7.87 (d, J = 8.2 Hz, 2 H), 7.92 (s, 2 H). 13C NMR (100 MHz, CDCl3): δ = 117.2, 121.0, 125.46, 125.58, 127.65, 127.72, 128.31, 128.47, 128.61, 129.31, 129.53, 129.62, 129.79, 130.59, 134.14, 134.26, 134.77, 148.15, 151.56, 161.01. HRMS (APCI): m/z [M + H]+ Calcd for C50H31O4: 695.2217; found: 695.2211