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Synlett 2011(2): 280-284  
DOI: 10.1055/s-0030-1259087
LETTER
© Georg Thieme Verlag Stuttgart ˙ New York

The Cobalt-Way to Heterophenylenes: Syntheses of 2-Thianorbiphenylenes, Monoazabiphenylenes, and Linear 1-Aza[3]phenylene {Biphenyleno[2,3-a]cyclobuta[1,2-b]pyridine}

Verena Engelhardta, J. Gabriel Garciaa, Aude A. Hubauda, Konstantin A. Lyssenkob, Spyros Spyroudisa, Tatiana V. Timofeevab, Paul Tongwab, K. Peter C. Vollhardt*a
a Department of Chemistry, University of California at Berkeley, Berkeley, CA 94720-1460, USA
Fax: +1(510)6435208; e-Mail: kpcv@berkeley.edu;
b Department of Natural Sciences, New Mexico Highlands University, Las Vegas, NM 87701, USA
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Publikationsverlauf

Received 19 October 2010
Publikationsdatum:
07. Dezember 2010 (online)

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Abstract

CpCo(CO)2 catalyzes the cocyclization of ortho-diethynylthiophenes and -pyridines with alkynes to construct the corresponding thia- and azaphenylenes. This strategy is applied to the synthesis of linear 1-aza[3]phenylene, the first higher heterophenylene.

Key words

alkynes - cobalt - cyclization - heterocycles - transition metals

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8

The structures of all new compounds (Scifinder) were in accord with their analytical and/or spectroscopic properties; see Supporting Information. CCDC 797197 and CCDC 797198 contain the supplementary crystallographic data for 12 and 14, respectively. These data can be obtained free of charge from The Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/data_request/cif.
Selected Data Compound 3a: colorless crystals; mp 80-81 ˚C (EtOH-H2O). IR (hexanes): 3010, 1364, 1250, 1064, 1031, 854 cm-¹. ¹H NMR (300 MHz, CDCl3): δ = 7.18 (s, 2 H), 6.53 (s, 2 H), 0.32 (s, 18 H). ¹³C NMR (75 MHz, CDCl3): δ = 148.2, 147.7, 144.8, 124.1, 113.2, 2.63. MS (EI, 70 eV): m/z (%) = 302 (100) [M]+, 273 (12), 272 (22), 271 (85), 215 (13), 73 (58). UV/Vis (EtOH): λmax (log ε) = 257 sh (5.04), 262 (5.16), 337 (4.37), 353 (4.43) nm. Anal. Calcd for C16H22SSi2: C, 63.51; H, 7.33. Found: C, 63.84; H, 7.58.
Compound 5: opaque oil. ¹H NMR (400 MHz, CDCl3): δ = 8.12 (d, J = 5 Hz, 1 H), 7.60 (br s, 1 H), 7.32 (s, 1 H), 7.27 (s, 1 H), 6.38 (d, J = 5 Hz, 1 H), 0.30 (s, 18 H). MS (EI, 70 eV): m/z (%) = 297 (100) [M]+, 282 (70), 266 (20), 239 (12), 73 (53). HRMS (EI): m/z [M]+ calcd for C17H23NSi2: 297.1369; found: 297.1361. UV/Vis (hexane): λmax (log ε) = 231 (3.56), 301 (3.02), 325 (3.25), 340 (3.31) nm.
Compound 7: opaque oil. ¹H NMR (500 MHz, CDCl3; assignments by 2D NMR): δ = 7.64 (d, J = 5.5 Hz, 1 H, H²), 7.26 (s, 1 H, H8), 7.16 (s, 1 H, H5), 6.74 (d, J = 6.5 Hz, 1 H, H4), 6.51 (dd, J = 6.25, 6.25 Hz, 1 H, H³), 0.34 (s, 9 H, Me3Si), 0.33 (s, 9 H, Me3Si). ¹³C NMR (100 MHz, CDCl3): δ = 173.1 (C8b), 152.7 (C8a), 150.9 (C6/7), 150.5 (C4b), 150.2 (C4a), 149.3 (C6/7), 145.7 (C²), 124.6 (C5), 124.3 (C8), 122.4 (C³), 122.0 (C4), 2.00 (SiCH3), 1.99 (SiCH3). MS (EI, 70 eV): m/z (%) = 297 (100) [M]+, 282 (72), 266 (32), 239 (17), 73 (55). HRMS (EI): m/z [M]+ calcd for C17H23NSi2: 297.1369; found: 297.1361. UV/Vis (hexane): λmax (log ε) = 241 (4.01), 270 (3.76), 347 (3.50), 362 nm (3.40).
Compound 14: deep red crystals; mp 225-226 ˚C (dec.; hexane). IR (neat): 3069, 2929, 2855, 1643, 1585, 1415, 1349, 1246, 1186, 1153, 865, 733 cm-¹. ¹H NMR (400 MHz, CDCl3; assignments by 2D NMR): δ = 7.48 (dd, J = 6.0, 1.2 Hz, 1 H, H²), 6.72 (m, 2 H, H7,8), 6.53 (m, 2 H, H6,9), 6.48 (d, J = 1.2 Hz, 1 H, H¹0), 6.45 (dd, J = 6.8, 1.2 Hz, 1 H, H4), 6.40 (s, 1 H, H5), 6.39 (dd, J = 6.4, 6.4 Hz, 1 H, H³). ¹³C NMR (150 MHz, CD2Cl2): δ = 172.2 (C¹0b), 155.4 (C4b/¹0a), 155.0 (C4b/¹0a), 153.9 (C5a/9b), 153.6 (C5a/9b), 150.4 (C5b/9a), 150.1 (C5b/9a), 148.9 (C4a), 145.2 (C²), 129.2 (C7/8), 129.0 (C7/8), 122.3 (C³), 119.2 (C4), 117.1 (C6/9), 117.0 (C6/9), 112.2 (C5), 111.4 (C¹0). MS (EI, 70 eV): m/z (%) = 227 (100) [M]+, 201 (30), 174 (7), 150 (4), 123 (3), 113 (14), 100 (22). HRMS (EI): m/z [M]+ calcd for C17H9N: 227.0735; found: 227.0739. UV/Vis (hexane): λmax (log ε) = 266 (5.48), 275 (5.60), 299 (4.97), 311 (4.91), 387 sh (4.68), 407 (5.07), 421 sh (5.02), 433 (5.28) nm.