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Synlett 2018; 29(03): 354-358
DOI: 10.1055/s-0036-1591489
letter
© Georg Thieme Verlag Stuttgart · New York

Cyclopropane Intermediates from Insertion Reactions of Platinum–Carbenes: A Route to Heterospiranes

Kiseong Kim
Department of Chemistry and Research Institute of Natural Science, Hanyang University, 222, Wangsimni-ro, Seongdong-gu, Seoul 04763, Republic of Korea   Email: changho@hanyang.ac.kr
,
Soyung Kim
Department of Chemistry and Research Institute of Natural Science, Hanyang University, 222, Wangsimni-ro, Seongdong-gu, Seoul 04763, Republic of Korea   Email: changho@hanyang.ac.kr
,
Chang Ho Oh*
Department of Chemistry and Research Institute of Natural Science, Hanyang University, 222, Wangsimni-ro, Seongdong-gu, Seoul 04763, Republic of Korea   Email: changho@hanyang.ac.kr
› Author AffiliationsFinancial support was provided by a grant from the National Research Foundation of Korea (NRF–2014R1A5A1011165).
Further Information

Publication History

Received: 30 July 2017

Accepted after revision: 14 September 2017

Publication Date:
11 October 2017 (online)

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Abstract

Heteroaromatic-anchored enynals with a pendent alkene group were successfully cyclized through a Huisgen-type [3+2] cycloaddition to give a tetracyclic Pt–carbene complex that underwent insertion into the C–H bond in the β-position to give fused cyclopropanes that are otherwise inaccessible. On heating, the cyclopropanes smoothly rearranged to form the corresponding heterospiranes with excellent levels of stereoselectivity and high yields.

Key words

cyclization - platinum catalysis - pyrylium ions - carbenes - heterospiranes

Supporting Information

    Supporting information for this article (copies of 1H and 13C NMR spectra for compounds 2b–g, 3b–c, 7a–c, 8a–e) is available online at https://doi.org/10.1055/s-0036-1591489.
  • Supporting Information
 

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  • 10 Heterocyclopropane 7a; Typical Procedure A new 5 mL test tube was charged with the 2-alkynylnicotinaldehyde 6a (0.40 mmol), PtCl2(PPh3)2 (11 mg, 0.04 mmol), and anhyd toluene (1.5 mL) at 0 °C under argon. The mixture was stirred for 4 h in a preheated oil bath (120 °C). When the reaction was complete (TLC), the solvent was removed under vacuum, and the crude product was purified by flash column chromatography (silica gel, hexane–EtOAc) to give a yellow oil; yield: 169 mg (94%); Rf = 0.41 (EtOAc–hexane, 1:4). IR (NaCl): 2980, 1732, 1440, 1244 cm–1. 1H NMR (400 MHz, CDCl3): δ = 7.92 (d, J = 8.0 Hz, 2 H), 7.49–7.46 (m, 2 H), 7.42 (d, J = 7.2 Hz, 1 H), 7.24 (d, J = 10.0 Hz, 1 H), 5.13 (d, J = 5.6 Hz, 1 H), 4.30–4.16 (m, 4 H), 3.12 (d, J = 15.2 Hz, 1 H), 2.45 (s, 1 H), 2.30 (d, J = 14.4 Hz, 2 H), 2.18–2.11 (m, 1 H), 1.93–1.78 (m, 3 H), 1.42 (d, J = 11.6 Hz, 1 H), 1.30 (t, J = 7.2 Hz, 3 H), 1.26 (t, J = 7.2 Hz, 3 H). 13C NMR (100 MHz, CDCl3): δ = 171.5, 170.8, 157.2, 154.6, 148.8, 148.7, 144.8, 144.7, 135.7, 135.6, 128.9, 128.8, 128.8, 128.5, 118.3, 118.1, 73.8, 61.9, 61.7, 61.7, 53.3, 33.7, 31.4, 30.7, 26.5, 22.8, 21.6, 14.2, 14.1. HRMS (ESI): m/z [M + Na]+ calcd for C26H26FNNaO5: 474.1688; found: 474.1691.
  • 11 Spiro(cyclohexane-1,7′-quinoline) 8a; Typical Procedure A new 5 mL test tube was charged with the 2-alkynylnicotinaldehyde 6a (0.40 mmol), PtCl2(PPh3)2 (11 mg, 0.04 mmol), and anhyd xylene (1.5 mL) at 0 °C under argon. The mixture was stirred for 1 h in a preheated oil bath (150 °C) until the reaction was complete (TLC). The solvent was removed under vacuum, and the crude product was purified by flash column chromatography (silica gel, hexane–EtOAc) to give a yellow oil; yield: 140 mg (78%); Rf  = 0.33 (EtOAc–hexane, 1:4). IR (NaCl): 2981, 1731, 1441, 1249, 1249 cm–1. 1H NMR (400 MHz, CDCl3): δ = 7.96 (d, J = 8.4 Hz, 2 H), 7.49–7.39 (m, 3 H), 7.13 (d, J = 11.2 Hz, 1 H), 6.52 (d, J = 9.2 Hz, 1 H) , 6.15 (d, J = 9.6 Hz, 1 H), 4.27–4.19 (m, 4 H), 3.36 (d, J = 16.0 Hz, 1 H), 3.10 (d, J = 16.0 Hz, 1 H), 2.92 (ABq, Δδ = 38.8 Hz, J = 15.2 Hz, 2 H), 2.44–2.28 (m, 2 H), 1.91–1.85 (m, 2 H), 1.26 (t, J = 7.2 Hz, 6 H). 13C NMR (100 MHz, CDCl3): δ = 207.0, 170.4, 170.1, 158.0, 155.4, 149.6, 149.5, 143.8, 143.7, 135.4, 135.4, 132.7, 132.6, 129.2, 129.1, 128.9, 128.9, 128.8, 128.8, 128.6, 127.9, 127.8, 126.3, 121.1, 120.9, 62.2, 62.2, 57.5, 50.6, 42.5, 38.4, 32.0, 26.0, 14.1. HRMS (ESI): m/z [M + Na]+calcd for C26H26FNNaO5: 474.1688; found: 474.1695.