Interconversions of aryl radicals by 1,4-shifts of hydrogen atoms. A synthesis of benzo[a]corannulene

Journal of the American Chemical Society

Volumn 127, Issue 47, 2005, Pages 16518-16521

  Peng, Lingqing ^a   Scott, Lawrence T ^a  

^a BOSTON COLLEGE   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

ATOMS; CHEMICAL BONDS; HIGH TEMPERATURE EFFECTS; HYDROGEN; SYNTHESIS (CHEMICAL); VACUUM;

ARYL CHLORIDES; HOMOLYSIS; HYDROGEN ATOMS; RADICAL PRECURSOR;

AROMATIC COMPOUNDS;

1 (2 CHLOROPHENYL)BENZO[GHI]FLUORANTHENE; 1 PHENYLBENZO[GHI]FLUORANTHENE; 2 (2 CHLOROPHENYL)BENZO[C]PHENANTHRENE; 2 (2,6 DICHLOROPHENYL)BENZO[C]PHENANTHRENE; ANNULENE DERIVATIVE; BENZO[A]CORANNULENE; CARBON; CHLORIDE; CHLORINE; HYDROGEN; PHENANTHRENE DERIVATIVE; POLYCYCLIC AROMATIC HYDROCARBON DERIVATIVE; RADICAL; UNCLASSIFIED DRUG;

AROMATIZATION; ARTICLE; ATOM; CHEMICAL BOND; CHEMICAL STRUCTURE; CYCLIZATION; DISSOCIATION; HIGH TEMPERATURE; PROTON TRANSPORT; PYROLYSIS; REACTION ANALYSIS; STEREOSPECIFICITY; STRUCTURE ANALYSIS; SYNTHESIS;

EID: 28444496044     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja054984+     Document Type: Article

References (16)

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2. Brooks, M. A.; Scott, L. T. J. Am. Chem. Soc. 1999, 121, 5444-5449.
3. 2
4. (b) An activation energy of 24 kcal/mol has been calculated for the 1,4-shift of hydrogen between the ortho and ortho' positions in the 2-biphenyl radical: Cioslowski, J.: Liu, G.; Moncrieff, D. J. Org. Chem. 1996, 61, 4111-4114.
5. The 2-bromo[4]helicene = 2-bromobenzo[c]phenanthrene was synthesized as described in ref 2.
6. 1H NMR spectrum of the mixture.
7. 5 of the various components.
8. Scott, L. T. Angew. Chem., Int. Ed. 2004, 43, 4994-5007.
9. The Suzuki-Miyaura couplings did not work as well in this more hindered case as it did for the syntheses of 1 and 5.
10. The closely related dibenzo[a,g]corannulene has been synthesized by a FVP route involving two aryl radical cyclizations of the type 7 → 8: (a) Bratcher, M. S.; Scott, L. T. In Abstracts of Papers, 207th National Meeting of the American Chemical Society: American Chemical Society: Washington, DC, March 1994, San Diego, CA.; abstr. ORGN 420.
11. (b) Bratcher, M. S., Ph.D. dissertation, Boston College, Chestnut Hill, MA, 1996.
12. Reisch, H. A.; Bratcher, M. S.; Scott, L. T. Org. Lett. 2000, 2, 1427-1430.
13. Mehta, G.; Srirama Sarma, P. V. V. Chem. Commun. 2000, 19-20.
14. See also: McComas, C. C.; Scott, L. T. In Abstracts of Papers, 211th National Meeting of the American Chemical Society, American Chemical Society: Washington, DC, March 1996, New Orleans, LA; abstr. CHED-556.
15. (a) Scott, L. T.; Bratcher, M. S.; Hagen, S. J. Am. Chem. Soc. 1996, 118, 8743-8744.
16. (b) Necula, A.; Scott, L. T. J. Anal. Appl. Pyrolysis 2000, 54, 65-87. A 4 cm section of the pyrolysis tube near the center of the hot zone was loosely packed with quartz wool in order to diminish the amount of starting material that passed through the tube without change.