Cross-conjugated oligothiophenes derived from the (C2S) n helix: Asymmetric synthesis and structure of carbon-sulfur [11]helicene

Journal of the American Chemical Society

Volumn 127, Issue 40, 2005, Pages 13806-13807

  Miyasaka, Makoto ^a   Rajca, Andrzej ^a   Pink, Maren ^b   Rajca, Suchada ^a  

^a UNIVERSITY OF NEBRASKA LINCOLN   (United States)

^b INDIANA UNIVERSITY   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

CARBON; SULFUR; THIOPHENE DERIVATIVE;

ANALYTIC METHOD; ARTICLE; ASYMMETRIC SYNTHESIS; CONJUGATION; DERIVATIZATION; MATERIAL STATE; OLIGOMERIZATION; PHOTOCHEMISTRY; PROTON NUCLEAR MAGNETIC RESONANCE; STRUCTURE ANALYSIS; X RAY ANALYSIS;

CARBON; CRYSTALLOGRAPHY, X-RAY; MAGNETIC RESONANCE SPECTROSCOPY; MODELS, MOLECULAR; MOLECULAR STRUCTURE; POLYCYCLIC COMPOUNDS; REFERENCE STANDARDS; SULFUR; THIOPHENES;

EID: 26444448373     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja055414c     Document Type: Article

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17. 1H NMR spectra are obtained with double solvent (ether) suppression, using samples from the preparative-scale reaction mixtures.
18. For the limiting ratios of 5 to 1, the isolated yield (and ee) for (-)-1 are 67% (ee 3%) and 19% (ee 25%). Determinations of ee are described in the Supporting Information.
19. -1) 294 (-122), 266 (-24), 257 (-44), 242 (53), 227 (-101), 212 (73), 200 (-14) (Figure S11).
20. D = -320 (-150); CD, one negative couplet (Figure S12).
21. (c) (-)-Helicenes and their axially chiral derivatives possessing negative couplet are expected to possess opposite configurations: Miyasaka, M.; Rajca, A.; Pink, M.; Rajca, S. Chem. Eur. J. 2004, 10, 6531-6539.
22. The only other example of tri-annelation is photochemical cobalt-catalyzed alkyne trimerization to [9]helicenes in 2-3.5% yields, ref 2e.
23. 2-mono- annelation is isolated as well.
24. 3-positions.
25. 2-tetradeuteration of 7 is observed upon lithiation with either near-stoichiometric (4.4 equiv) or excess (6.4 equiv) amount of n-BuLi in the presence of (-)-sparteine, followed by addition of MeOD.
26. Analogous LDA/(-)-sparteine-mediated di-annelation of hexathiophene (obtained by cross-coupling of 4,4′-dibromo-dithieno[2,3-b:3′, 2′-d]-thiophene and 2-octyl-5-bromothiophene) gives [7]helicene 2 in ∼20% yields. Synthetic details pertaining to 2 and its gelator properties will be reported elsewhere.
27. 4);
28. 4);
29. 4).
30. 2 of only 0.98 are used.