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}

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.

alkynes - cobalt - cyclization - heterocycles - transition metals

References and Notes

For a review, see:

1a Miljanić OŠ. Vollhardt KPC. In Carbon-Rich Compounds: From Molecules to Materials   Haley MM. Tykwinski RR. Wiley-VCH; Weinheim: 2006.  p.140 

See also:

1b Mohler DL. Kumaraswamy S. Stanger A. Vollhardt KPC. Synlett  2006,  2981 

For selected references and patents, see:

2a Nakatsuka M. inventors; JP 2010219301 A  20100930.  ; Chem. Abstr. 2010, 153, 446064

2b Kano T, Suzuki K, and Nakada S. inventors; JP 2010146833 A  20100701.  ; Chem. Abstr. 2010, 153, 130239

2c Schmälzlin E, Eich S, Dosche C, and Löhmannsröben H.-G. inventors; DE 102008044317 A1  20100617.  ; Chem. Abstr. 2010, 153, 52277

2d Schmälzlin E, Eich S, Dosche C, and Löhmannsröben H.-G. inventors; WO 2010063806 A1  20100610.  ; Chem. Abstr. 2010, 153, 52265

2e Watanabe M, and Ohashi T. inventors; JP 2010070473 A  20100402.  ; Chem. Abstr. 2010, 152, 405420

2f Thalacker C, Hailand B, Dede K, and Eckert AS. inventors; WO 2009152211 A2  20091217.  ; Chem. Abstr. 2009, 152, 76163

2g Watanabe M, and Ohashi T. inventors; JP 2008247853 A  20081016.  ; Chem. Abstr. 2008, 149, 471208

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For selected very recent advances in the topologically relevant heteroacenes, see:

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5b Santato C. Favaretto L. Melucci M. Zanelli A. Gazzano M. Monari M. Isik D. Banville D. Bertolazzi S. Loranger S. Cicoira F. J. Mater. Chem.  2010,  20:  669 

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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): 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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18a Garcia Y. Schoenebeck F. Legault CY. Merlic CA. Houk KN. J. Am. Chem. Soc.  2009,  131:  6632 

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21b Hull R. MacBride JAH. Wright PM. J. Chem. Res., Synop.  1984,  328 ; J. Chem. Res., Miniprint 1984, 3001

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

22a 1,8-Diazabiphenylene: Deroski BR. Ricci JS. MacBride JAH. Markgraf JH. Can. J. Chem.  1984,  62:  2235 

22b N-Allyl-2,7-diazabiphenylenium bromide: Kanoktanaporn S. MacBride JAH. King TJ. J. Chem. Res., Synop.  1980,  204 ; J. Chem. Res., Miniprint 1980, 2911

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