Practical Syntheses of N-Hexylcarbazol-2-yl- and -3-yl-boronic Acids, Their Cross-Coupled Products and a Derived Tris-cyclometalated (Pyridin-2-yl)carbazole Iridium(III) Complex

Mustafa Tavasli; Sylvia Bettington; Martin R. Bryce; Andrei S. Batsanov; Andrew P. Monkman

doi:10.1055/s-2005-865307

Subscribe to RSS

Please copy the URL and add it into your RSS Feed Reader.

https://www.thieme-connect.de/rss/thieme/en/10.1055-s-00000084.xml

Share / Bookmark

Facebook X Linkedin Weibo

Download PDF

Synthesis 2005(10): 1619-1624
DOI: 10.1055/s-2005-865307

PAPER

Practical Syntheses of N-Hexylcarbazol-2-yl- and -3-yl-boronic Acids, Their Cross-Coupled Products and a Derived Tris-cyclometalated (Pyridin-2-yl)carbazole Iridium(III) Complex

Mustafa Tavasli^a, Sylvia Bettington^a, Martin R. Bryce*^a, Andrei S. Batsanov^a, Andrew P. Monkman^b
^a Department of Chemistry, University of Durham, South Road, Durham, DH1 3LE, UK
Fax: +44(191)3844737; e-Mail: m.r.bryce@durham.ac.uk;
^b Department of Physics, University of Durham, South Road, Durham, DH1 3LE, UK

Further Information

Publication History

Received 10 January 2005
Publication Date:
12 April 2005 (online)

Abstract
Full Text
References

Permissions and Reprints All articles of this category

Abstract

The syntheses of N-hexylcarbazol-2-yl- and -3-yl-boronic acids (1 and 2) are described on a ca. 7 g scale, starting from commercially available 2,5-dibromonitrobenzene (4) and carbazole (11), respectively. Compounds 1 and 2 underwent efficient palladium-catalyzed cross-coupling reactions under Suzuki-Miyaura conditions to yield products 17, 18 and 20. Compound 18 reacted with IrCl₃ to give the tris-cyclometalated (pyridin-2-yl)carbazole iridium(III) complex 21, the X-ray crystal structure of which is reported.

Key words

carbazole - boronic acid - fluorene - cross-coupling reaction - cyclometalating ligands - iridium complex

References

1 Review: Knölker H.-J. Reddy KR. Chem. Rev. 2002, 102: 4303

Crossref PubMed Google Scholar
2 Nagarajan R. Perumal PT. Synthesis 2004, 1269 ; and references cited therein

Article in Thieme Connect Google Scholar
3 Wakim S. Bouchard J. Blouin N. Michaud A. Leclerc M. Org. Lett. 2004, 6: 3413

Crossref Google Scholar
4a Review: Zhang Y. Wada T. Sasabe H. J. Mater. Chem. 1998, 8: 809

Crossref Google Scholar
4b Belloni M. Manickam M. Preece JA. Ferroelectrics 2002, 276: 103

Crossref Google Scholar
5a Manickam M. Cooke G. Kumar S. Ashton PR. Preece JA. Spencer N. Mol. Cryst. Liq. Cryst. 2003, 397: 399

Crossref Google Scholar
5b Perea E. Lopez-Calahorra F. Velasco D. Liq. Cryst. 2002, 29: 421

Crossref Google Scholar
6 Bouchard J. Wakim S. Leclerc M. J. Org. Chem. 2004, 69: 5705

Crossref Google Scholar
7a Cho NS. Hwang D.-H. Jung B.-J. Oh J. Chu HY. Shim H.-K. Synth. Met. 2004, 143: 277

Crossref Google Scholar
7b Kim BS. Joo S.-H. Oh D. Cha SW. Choi DS. Lee CE. Jin J.-I. Synth. Met. 2004, 145: 229

Crossref Google Scholar
7c van Dijken A. Bastiaansen JJAM. Kiggen NMM. Langeveld BMW. Rothe C. Monkman AP. Bach I. Stossel P. Brunner K. J. Am. Chem. Soc. 2004, 126: 7718

Crossref Google Scholar
8 Dierschke F. Grimsdale AC. Müllen K. Macromol. Chem. Phys. 2004, 205: 1147

Crossref Google Scholar
9 Miyaura N. Suzuki A. Chem. Rev. 1995, 95: 2457

Google Scholar
10a Cadogan JIG. Cameron-Wood M. J. Chem. Soc. 1962, 361

Article in Thieme Connect Google Scholar
10b Cadogan JIG. Cameron-Wood M. Mackie RK. Searle RJG. J. Chem. Soc. 1965, 4831

Article in Thieme Connect Google Scholar
10c Morin J.-F. Leclerc M. Macromolecules 2001, 34: 4680

Article in Thieme Connect Google Scholar
10d Dierschke F. Grimsdale AC. Müllen K. Synthesis 2003, 2470

Article in Thieme Connect Google Scholar
11 Percec V. Obata M. Rudic JG. De B B. Glodde M. Bera TK. Magonow SN. Balagurusamy VSK. Heiney PA. J. Poly. Sci. Part A, Polym. Chem. 2002, 40: 3509

Crossref Google Scholar
12 Li Y. Ding J. Day M. Tao Y. Lu J. D’iorio M. Chem. Mater. 2004, 16: 2165

Crossref Google Scholar
13a Kuroki M. Kogyo Kagaku Zasshi 1967, 70: 63 ; Chem. Abstr. 1968, 68, 12802

Crossref Google Scholar
13b Pielichowski J. Kyzio J. Monatsh. Chem. 1974, 105: 1306

Crossref Google Scholar
13c Ribou A.-C. Wada T. Sasabe H. Inorg. Chim. Acta. 1999, 288: 134

Crossref Google Scholar
14 Smith MB. Guo L(C.). Okeyo S. Stenzel J. Yanella J. LaChapelle E. Org. Lett. 2002, 4: 2321

Crossref Google Scholar
15a Spanggaard H. Jørgensen M. Almdal K. Macromolecules 2003, 36: 1701

Crossref Google Scholar
15b Smith K. James DM. Mistry AG. Bye MR. Faulkner DJ. Tetrahedron 1992, 48: 7479

Crossref Google Scholar
15c Bogdal D. Lukasiewicz M. Pielichowski J. Green Chem. 2004, 6: 110

Crossref Google Scholar
16 Paliulis O. Ostrauskaite J. Gaidelis V. Jankauskas V. Strohriegl P. Macromol. Chem. Phys. 2003, 204: 1706

Crossref Google Scholar
17 Tavasli M. Bettington S. Bryce MR. Al Attar HA. Dias FB. King S. Monkman AP. manuscript submitted
18 Konno H. Sasaki Y. Chem. Lett. 2003, 32: 252

Crossref Google Scholar
19 For structurally different cyclometalated carbazole derivatives, see: Igawa S., Takiguchi T., Kamatani A., Okada S., Tsuboyama A., Miura K., Moriyama T., Iwawaki H.; Japanese Patent 2003342284, 2002; Chem. Abstr. 2004, 140, 21334
20 For a different synthesis of 5 with no reported spectroscopic data, see: Badger GM. Sasse WFH. J. Chem. Soc. 1957, 4

Google Scholar

21

CCDC No.: 257962. Supplementary data available in CIF format from the authors.

22

Compound 21, CCDC No.: 260850; compound 21·2CH₂Cl₂·0.5Me₂CO, CCDC No.: 260851. Supplementary data available in CIF format from the authors.