Palladium-Catalysed Sonogashira Reactions of 16-(Hydroxymethylidene)-3-methoxy-α-estrone

Stefan Jopp; Marko Liesegang; Peter Ehlers; Eva Frank; Gyula Schneider; János Wölfling; Alexander Villinger; Peter Langer

doi:10.1055/s-0036-1588537

Synlett, Inhaltsverzeichnis

Synlett 2017; 28(19): 2647-2649
DOI: 10.1055/s-0036-1588537

letter

Palladium-Catalysed Sonogashira Reactions of 16-(Hydroxymethylidene)-3-methoxy-α-estrone

Authors

Stefan Jopp

^aUniversität Rostock, Institut für Chemie, Albert-Einstein-Str. 3a, 18059 Rostock, Germany eMail: peter.langer@uni-rostock.de
Marko Liesegang

^aUniversität Rostock, Institut für Chemie, Albert-Einstein-Str. 3a, 18059 Rostock, Germany eMail: peter.langer@uni-rostock.de
Peter Ehlers

^aUniversität Rostock, Institut für Chemie, Albert-Einstein-Str. 3a, 18059 Rostock, Germany eMail: peter.langer@uni-rostock.de

^bLeibniz-Institut für Katalyse e.V. an der Universität Rostock, Albert-Einstein-Str. 29a, 18059 Rostock, Germany
Eva Frank

^cDepartment of Organic Chemistry, University of Szeged, Dóm tér 8, 6720 Szeged, Hungary
Gyula Schneider

^cDepartment of Organic Chemistry, University of Szeged, Dóm tér 8, 6720 Szeged, Hungary
János Wölfling

^cDepartment of Organic Chemistry, University of Szeged, Dóm tér 8, 6720 Szeged, Hungary
Alexander Villinger

^aUniversität Rostock, Institut für Chemie, Albert-Einstein-Str. 3a, 18059 Rostock, Germany eMail: peter.langer@uni-rostock.de
Peter Langer*

^aUniversität Rostock, Institut für Chemie, Albert-Einstein-Str. 3a, 18059 Rostock, Germany eMail: peter.langer@uni-rostock.de

^bLeibniz-Institut für Katalyse e.V. an der Universität Rostock, Albert-Einstein-Str. 29a, 18059 Rostock, Germany

Abstract

Alle Artikel dieser Rubrik

Abstract

Sonogashira reactions of steroids have been studied. The reaction of α-estron-16-methylidenyloxy triflate with various alkynes afforded novel alkynylvinylidene steroids. The reactions proceeded in good to quantitative yields, with excellent E-selectivity and with a broad synthetic scope.

Key words

estrone - steroids - Sonogashira coupling - palladium - alkynes

Volltext

Referenzen

References and Notes
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6 Suffert J. Brückner R. Tetrahedron Lett. 1991; 32: 1453
7 CCDC 1553798 contains supplementary crystallographic data. These data can be obtained free of charge from The Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/getstructures.
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9 (E)-16-(3-Phenylprop-2-ynylidene)-3-methoxy-α-estrone (3a) Compound 2 (0.225 mmol, 100 mg), CuI (0.006 mmol, 2.5 mol%, 1.1 mg), Pd(OAc)₂ (0.006 mmol, 2.5 mol%, 1.3 mg), XPhos (0.012 mmol, 5.0 mol%, 5.7 mg), and phenylacetylene (0.338 mmol, 35 mg) were dissolved in THF (5 mL) and NEt₃ (1 mL). The reaction mixture was stirred at r.t. for 6 h. The solution was diluted with H₂O and extracted with EtOAc (3×). The crude product was purified by column chromatography on silica (elution system heptane/EtOAc, 20:1). Yield: 86 mg (97%); mp 54–55 °C. ¹H NMR (250 MHz, CDCl₃): δ = 0.79–0.88 (m, 3 H), 1.10 (s, 3 H, Me), 1.43–1.51 (m, 2 H), 1.76–1.83 (m, 1 H), 2.09–2.17 (m, 1 H), 2.24–2.32 (m, 2 H), 2.40–2.48 (m, 1 H), 2.79–2.92 (m, 3 H), 3.76 (s, 3 H, OMe), 6.59 (d, ⁴ J = 2.71 Hz, 1 H), 6.67–6.72 (m, 2 H), 7.18 (d, ³ J = 8.58 Hz, 1 H), 7.36–7.39 (m, 3 H), 7.50–7.54 (m, 2 H).¹³C NMR (63 MHz, CDCl₃): δ = 25.5 (CH₃), 28.1, 28.3, 29.9, 30.3, 32.2 (CH₂), 41.3, 43.0, 47.6 (CH), 50.8 (C), 55.2 (OCH₃), 87.2, 101.0 (C≡C), 111.7, 113.5, 114.5 (CH), 122.7 (C), 126.9, 128.5, 129.2 (CH), 131.8 (C), 131.9 (CH), 138.0, 146.1, 157.5 (C), 207.4 (C=O). IR (ATR,): 2918 (w), 2187 (w), 1711 (w), 1609 (w), 1498 (w), 1448 (w), 1257 (m), 1076 (m), 1016 (s), 870 (w), 793 (s), 755 (m), 688 (m), 531 (w) cm^–1. MS (EI, 70 eV): m/z (%) = 397 (16), 396 (M⁺, 78), 227 (15), 210 (14), 186 (10), 178 (11), 174 (15), 173 (12), 165 (24), 160 (14), 158 (13), 153 (13), 152 (12), 147 (11), 145 (15), 144 (11), 141 (23), 140 (100), 139 (96), 129 (16), 128 (17), 126 (17), 115 (25), 114 (18), 102 (18), 91 (21), 65 (11). ESI-HRMS: m/z calcd for C₂₈H₂₉O [M + H⁺]: 397.21621; found: 397.21644.

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