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 Engelhardt; J. Gabriel Garcia; Aude A. Hubaud; Konstantin A. Lyssenko; Spyros Spyroudis; Tatiana V. Timofeeva; Paul Tongwa; K. Peter C. Vollhardt

doi:10.1055/s-0030-1259087

LETTER

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 Engelhardt^a, J. Gabriel Garcia^a, Aude A. Hubaud^a, Konstantin A. Lyssenko^b, Spyros Spyroudis^a, Tatiana V. Timofeeva^b, Paul Tongwa^b, 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

Abstract

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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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References

References and Notes

For a review, see:

<A NAME="RS07710ST-1A">1a</A> Miljanić OŠ. Vollhardt KPC. In Carbon-Rich Compounds: From Molecules to Materials Haley MM. Tykwinski RR. Wiley-VCH; Weinheim: 2006. p.140

See also:

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For selected references and patents, see:

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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): λ_max (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): λ_max (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, H^²), 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, H^³), 0.34 (s, 9 H, Me₃Si), 0.33 (s, 9 H, Me₃Si). ^¹³C NMR (100 MHz, CDCl₃): δ = 173.1 (C^8b), 152.7 (C^8a), 150.9 (C^6/7), 150.5 (C^4b), 150.2 (C^4a), 149.3 (C^6/7), 145.7 (C^²), 124.6 (C⁵), 124.3 (C⁸), 122.4 (C^³), 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): λ_max (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, H^²), 6.72 (m, 2 H, H^7,8), 6.53 (m, 2 H, H^6,9), 6.48 (d, J = 1.2 Hz, 1 H, H^¹0), 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, H^³). ^¹³C NMR (150 MHz, CD₂Cl₂): δ = 172.2 (C^¹0b), 155.4 (C^4b/¹0a), 155.0 (C^4b/¹0a), 153.9 (C^5a/9b), 153.6 (C^5a/9b), 150.4 (C^5b/9a), 150.1 (C^5b/9a), 148.9 (C^4a), 145.2 (C^²), 129.2 (C^7/8), 129.0 (C^7/8), 122.3 (C^³), 119.2 (C⁴), 117.1 (C^6/9), 117.0 (C^6/9), 112.2 (C⁵), 111.4 (C^¹0). 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): λ_max (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.

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There are only two X-ray crystallographic structure determinations of azabiphenylene derivatives.

<A NAME="RS07710ST-22A">22a</A> 1,8-Diazabiphenylene: Deroski BR. Ricci JS. MacBride JAH. Markgraf JH. Can. J. Chem. 1984, 62: 2235

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Supplementary Material

Supporting Information