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Synlett 2009(2): 201-204  
DOI: 10.1055/s-0028-1087395
LETTER
© Georg Thieme Verlag Stuttgart ˙ New York

First Synthesis of Functionalized Benzonitriles by Formal [3+3] Cyclocondensations of 1,3-Bis(silyloxy)buta-1,3-dienes

Olumide Fatunsina, Mohanad Shkoora, Abdolmajid Riahia,b, Rüdiger Dedea, Helmut Reinkea, 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: +049(381)4986412; e-Mail: peter.langer@uni-rostock.de;
Further Information

Publication History

Received 22 September 2008
Publication Date:
15 January 2009 (online)

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Abstract

A variety of functionalized benzonitriles were regioselectively prepared by formal [3+3] cyclocondensation of 1,3-bis(silyloxy)buta-1,3-dienes with 3-ethoxy- and 3-silyloxy-2-cyano-2-en-1-ones.

Key Words

arenas - benzonitriles - cyclizations - regioselectivity - silyl enol ethers

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17

Typical Experimental Procedure for the Synthesis of 4a-l To a stirred solution of CH2Cl2 (3 mL per 1.0 mmol of 2a-e) of 2a-e was added 3a-h (1.1 mmol) and, subsequently, TiCl4 (1.1 mmol) at -78 ˚C under argon atmosphere. The temperature of the reaction mixture was allowed to rise to 20 ˚C over 14 h with stirring. To the solution was added HCl (10%, 20 mL) and the organic and the aqueous layer were separated. The latter was extracted with CH2Cl2 (3 × 20 mL). The combined organic layers were dried (Na2SO4), filtered, and the filtrate was concentrated in vacuo. The residue was purified by column chromatography (SiO2, heptanes-EtOAc) to give 4a-l. Starting with 2a (0.209 g, 1.5 mmol) and 3a (0.446 g, 1.65 mmol), 4a was isolated as a colorless solid (101 mg, 33%), mp 86-87 ˚C. ¹H NMR (250 MHz, CDCl3): δ = 1.39 (t, ³ J = 7.1 Hz, 3 H, OCH2CH 3), 2.72 (s, 3 H, CH3), 4.42 (q, ³ J = 7.1 Hz, 2 H, OCH 2CH3), 6.84 (d, ³ J = 8.8 Hz, 1 H, Ar), 7.53 (d, ³ J = 8.8 Hz, 1 H, Ar), 11.78 (s, 1 H, OH). ¹³C NMR (75 MHz, CDCl3): δ = 13.1 (CH3), 20.8 (OCH2 CH3), 61.7 (OCH2), 104.8 (CCN), 112.6 (CCO2Et), 116.0 (CH), 117.4 (CN), 136.7 (CH), 145.5 (CCH3), 164.8 (COH), 169.6 (C=O). IR (neat): ν = 3072 (w), 2991 (w), 2923 (w), 2851 (w), 2777 (w), 2692 (w), 2589 (w), 2224 (w), 1660 (s), 1588 (m), 1570 (w), 1476 (m), 1450 (w), 1398 (m), 1375 (s), 1348 (m), 1318 (m), 1302 (m), 1231 (s), 1182 (w), 1146 (m), 1108 (w), 1057 (w), 1021 (m), 996 (w), 909 (w), 856 (m), 831 (m), 723 (w), 632 (w), 609 (w), 558 (w) cm-¹. MS (GC-MS, 70 eV): m/z (%) = 205 (26) [M+], 159 (100), 130 (22), 103 (8), 77 (12), 51 (6). HRMS (EI): m/z calcd for C11H11NO3: 205.07334; found: 205.073572.

18

CCDC-703181 contains 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 Crystallo-graphic Data Centre, 12 Union Road, Cambridge, CB2 1EZ, UK; fax: +44 (1223)336033; or deposit@ccdc.cam.ac.uk.

20

Typical Experimental Procedure for the Synthesis of 6a-f To a CH2Cl2 solution of 5 was added TiCl4 at -78 ˚C in the presence of MS (4 Å). The appropriate bis(silyl enol ether) 3 was subsequently added. The reaction mixture was allowed to warm to 20 ˚C during 20 h and was stirred for further 4 h. To the solution was added CH2Cl2, the MS were removed, and a sat. aq soln of NaHCO3 was added. The organic layer was separated, and the aqueous layer was repeatedly extracted with CH2Cl2. All organic extracts were combined, dried (Na2SO4), and filtered. The filtrate was concentrated in vacuo. The residue was purified by column chromatography (SiO2) to give salicylates 6. Starting with 5 (188 mg, 0.95 mmol), CH2Cl2 (3.0 mL), MS (4 Å, 0.4 g), TiCl4 (0.11 mL, 1.0 mmol), and 3i (356 mg, 1.4 mmol), compound 6a was isolated by column chromatography (SiO2; n-heptane-EtOAc, 10:1) as a colorless solid (67 mg, 34%), mp 109-110 ˚C; R f  = 0.21 (n-heptane-EtOAc, 10:1); reaction time 21 h. ¹H NMR (250 MHz, CDCl3): δ = 2.48 (d, 4 J = 0.9 Hz, 3 H, ArCH3), 2.75 (s, 3 H, ArCH3), 3.98 (s, 3 H, OCH3), 6.76 (s, 1 H, CHAr), 11.72 (s, 1 H, OH). ¹³C NMR (75 MHz, CDCl3): δ = 21.4, 21.8 (ArCH3), 52.7 (OCH3), 107.0, 111.0, 117.3 (2 × CAr, CN), 117.4 (CHAr), 146.6, 148.4 (CAr), 165.1, 171.0 (CArOH, CO). IR (KBr): ν = 3431 (br, m), 2957 (m), 2217 (s), 1668 (s), 1601 (s), 1581 (s), 1442 (s), 1368 (s), 1358 (s), 1319 (s), 1241 (s), 810 (s) cm-¹. MS (EI, 70 eV): m/z (%) = 205 (83) [M+], 174 (76), 173 (100), 145 (66), 144 (37), 116 (20), 91 (14). Anal. Calcd for C11H11NO3 (205.21): C, 64.38; H, 5.40; N, 6.83. Found: C, 64.64; H, 5.52; N, 6.65.