First Site-Selective Suzuki-Miyaura
Reactions of 2,3,4-Tribromothiophene

Serge-Mithérand Tengho Toguem; Alexander Villinger; Peter Langer

doi:10.1055/s-0029-1219380

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Synlett 2010(6): 909-912
DOI: 10.1055/s-0029-1219380

LETTER

First Site-Selective Suzuki-Miyaura Reactions of 2,3,4-Tribromothiophene

Serge-Mithérand Tengho Toguem^a, Alexander Villinger^a, Peter Langer*^a,b
^a Institut für Chemie, Universität Rostock, Albert Einstein Str. 3a, 18059 Rostock, Germany
^b Leibniz-Institut für Katalyse an der Universität Rostock e.V., Albert Einstein Str. 29a, 18059 Rostock, Germany
Fax: +1(381)4986412; e-Mail: peter.langer@uni-rostock.de;

Further Information

Publication History

Received 5 December 2009
Publication Date:
08 February 2010 (online)

Abstract
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Abstract

The first Suzuki-Miyaura reactions of 2,3,4-tribromothiophene are reported. These reactions provide a convenient and site-selective approach to 2-aryl-3,4-dibromothiophenes, 2,4-diaryl-3-bromothiophenes, and 2,3,4-triarylthiophenes.

Key words

catalysis - palladium - Suzuki-Miyaura reaction - site selectivity - thiophene

References and Notes

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General Procedure for the Synthesis of 2-Aryl-3,4-dibromothiophenes 2
To a mixture of 1 (0.159 g, 0.5 mmol), arylboronic acid (0.55 mmol), Pd(PPh₃)₄ (5 mol%) were added a mixture of 1,4-dioxane and toluene (1:1, 5 mL) and an aq solution of K₂CO₃ (2 mL, 2 M) under argon atmosphere. The reaction mixture was stirred at 100 ˚C for 5 h and was subsequently allowed to cool to 20 ˚C. The solution was poured into H₂O and CH₂Cl₂ (25 mL each), and the organic and the aqueous layer were separated. The latter was extracted with CH₂Cl₂ (3 × 25 mL), dried (Na₂SO₄), filtered, and concentrated in vacuo. The residue was purified by flash column chromatography (flash silica gel, heptanes).
Synthesis of 3,4-Dibromo-2-(4-ethylphenyl)thio-phene (2b)
Starting with 1 (0.320 g, 1.0 mmol) and 4-ethylphenyl- boronic acid (0.165 g, 1.1 mmol), 2b was isolated (0.298 g, 87%) as a colorless oil. ^¹H NMR (300 Hz, CDCl₃): δ = 1.32 (t, ^³ J = 7.6 Hz, 3 H, CH₃), 2.75 (q, ^³ J = 7.6 Hz, 2 H, CH₂), 7.32 (d, ^³ J = 8.4 Hz, 2 H, Ar), 7.38 (s, 1 H, Ar), 7.58 (d, ^³ J = 8.3 Hz, 2 H, Ar). ^¹³C NMR (62 MHz, CDCl₃): δ = 15.4 (CH₃), 28.7 (CH₂), 111.0, 114.7 (CBr), 122.0 (CH, thiophene), 128.2 (2 CH, Ar), 128.9 (2 CH, Ar), 130.3, 139.7, 145.7 (C). IR (KBr): ν = 3107 (w), 3020 (w), 2961 (m), 2927 (m), 2630 (w), 2306 (w), 1903 (w), 1524 (w), 1484 (m), 1308 (w), 1126 (w), 963 (w), 877 (s), 828 (s), 785 (m), 722 (s), 645 (w), 585 (m), 539 (m) cm^-¹. GC-MS (EI, 70 eV): m/z (%) = 348 (44) [M⁺, ^8¹Br, ^8¹Br], 346 (83) [M⁺, ^8¹Br, ⁷⁹Br], 344 (41) [M⁺, ⁷⁹Br, ⁷⁹Br], 333 (54), 331 (100) [M⁺], 329 (50), 186 (11), 171 (38), 139 (11). HRMS (EI, 70 eV): m/z calcd for C₁₂H₁₀Br₂S [M⁺, Br, ^8¹Br]: 345.88440; found: 345.88457.

11

CCDC 760153 and 760154 contain all crystallographic details of this publication and is available free of charge at www.ccdc.cam.ac.uk/conts/retrieving.html or can be ordered from the following address: Cambridge Crystallographic Data Centre, 12 Union Road, Cambridge CB21EZ; Fax: +44 (1223)336033; or deposit@ccdc.cam.ac.uk.