Hydrothiolation of Donor–Acceptor Cyclopropanes through Er(OTf)3-Promoted Three-Component Ring-Opening Reaction

S. Sina Hosseini; Aida Abdi; Ali Nikbakht; Hamid Reza Bijanzadeh; Frank Rominger; Daniel B. Werz; Saeed Balalaie

doi:10.1055/a-1760-8951

Synlett, Table of Contents

Synlett 2022; 33(05): 468-472
DOI: 10.1055/a-1760-8951

letter

Hydrothiolation of Donor–Acceptor Cyclopropanes through Er(OTf)₃-Promoted Three-Component Ring-Opening Reaction

S. Sina Hosseini

^aPeptide Chemistry Research Center, K. N. Toosi University of Technology, P. O. Box 15875-4416, Tehran, Iran

,

Aida Abdi

^aPeptide Chemistry Research Center, K. N. Toosi University of Technology, P. O. Box 15875-4416, Tehran, Iran

,

Ali Nikbakht

^aPeptide Chemistry Research Center, K. N. Toosi University of Technology, P. O. Box 15875-4416, Tehran, Iran

,

Hamid Reza Bijanzadeh

^bDepartment of Environmental Sciences, Faculty of Natural Resources and Marine Sciences, Tarbiat Modares University, Tehran 19697, Iran

,

Frank Rominger

^cOrganisch-Chemisches Institut der Universität Heidelberg, Im Neuenheimer Feld 271, 69120 Heidelberg, Germany

,

Daniel B. Werz∗

^dTechnische Universität Braunschweig, Institute of Organic Chemistry, Hagenring 30, 38106 Braunschweig, Germany

,

Saeed Balalaie ∗

^aPeptide Chemistry Research Center, K. N. Toosi University of Technology, P. O. Box 15875-4416, Tehran, Iran

› Author Affiliations

Abstract

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Abstract

A novel ring-opening reaction of donor–acceptor cyclopropanes (DACs) through a one-pot three-component nucleophilic addition of amines, CS₂, and DACs has been described. New γ-dithiocarbamate dialkyl malonate skeletons were obtained in up to 97% yield.

Key words

donor–acceptor cyclopropanes - hydrothiolation - ring-opening reaction - three-component reaction

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References

References and Notes

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12 Dithiocarbamates 4a–o: General ProcedureTo a mixture of carbon disulfide 2 (0.6 mmol, 2 equiv) and toluene (3 mL) as a solvent, amine 1a–f (0.3 mmol) was added, and the mixture was stirred for 30 min at ambient temperature. Then the donor–acceptor cyclopropane 3a–j (0.3 mmol) and Er(OTf)₃ (18 mg, 10 mol%) as a Lewis acid was added, and the mixture was heated at 90 °C for 4 h. After completion, the solvent was removed in vacuo, and the products were purified by flash column chromatography using n-hexane/EtOAc (8:1) as an eluent to give dithiocarbamates 4a–o. Dimethyl 2-{2-phenyl-2-[(piperidine-1-carbonothioyl)-thio]ethyl}malonate (4a)Colorless solid; mp 130–131 °C (96 mg , yield 82%, silica gel, n-hexane/EtOAc = 8:1). ¹H{¹³C} NMR (CDCl₃, 300 MHz): δ = 7.41–7.28 (m, 5 H, HAr), 5.27 (dd, J = 8.6, 2.2 Hz, 1 H, SCH), 4.25 (br s, 2 H, NCH_eq), 3.84 (br s, 2 H, NCH_ax), 3.78 (s, 3 H, OMe), 3.59 (s, 3 H, OMe), 3.44 (t, J = 7.3 Hz, 1 H, CH), 2.83–2.61 (m, 2 H, CH₂), 1.60–1.70 (m, 6 H, 3(CH₂)) ppm. ¹³C{¹H} NMR (CDCl₃, 75 MHz): δ = 193.5, 169.2, 169.1, 139.5, 128.7, 128.3, 127.8, 53.7, 52.7, 52.5, 50.0, 35.2, 25.9, 25.4, 24.2 ppm. HRMS-ESI: m/z calcd for C₁₉H₂₆NO₄S₂ [M + H]⁺: 396.1297; found: 396.1296.
13 CCDC 2130147 and 2130148 contain the supplementary crystallographic data for this paper. The data can be obtained free of charge from The Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/structures.

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