Facile Synthesis of Functionalized Oligophenothiazines via One-Pot Bromine-Lithium Exchange-Borylation-Suzuki Coupling (BLEBS)

Abstract

The bromine-lithium exchange in bromophenothiazines followed by transmetalation with trimethyl borate and addition of palladium catalyst, 1.2 equivalents of a base, and an aryl halide yields the cross-coupling products in moderate to very good yields.

borylations - cross-coupling - heterocycles - metalation - oligomers - one-pot reactions

References

<A NAME="RT16907SS-1">1</A> Sainsbury M. In Comprehensive Heterocyclic Chemistry   Vol. 3:  Katritzky AR. Rees CW. Pergamon; Oxford: 1984.  p.995 

<A NAME="RT16907SS-2A">2a</A> Mietzsch F. Angew. Chem.  1954,  66:  363 

<A NAME="RT16907SS-2B">2b</A> Ionescu M. Mantsch H. Adv. Heterocycl. Chem.  1967,  8:  83 

<A NAME="RT16907SS-2C">2c</A> Bodea C. Silberg I. Adv. Heterocycl. Chem.  1968,  9:  321 

<A NAME="RT16907SS-2D">2d</A> Valzelli L. Garattini S. In Principles of Psychopharmacology   Clark WG. Academic Press; New York: 1970.  p.255 

<A NAME="RT16907SS-2E">2e</A> Okafor CO. Heterocycles  1977,  7:  391 

<A NAME="RT16907SS-2F">2f</A> Eckstein Z. Urbanski T. Adv. Heterocycl. Chem.  1978,  23:  1 

<A NAME="RT16907SS-2G">2g</A> Szabo J. Chem. Heterocycl. Compd. USSR (Engl. Trans.)  1979,  15:  291 

<A NAME="RT16907SS-2H">2h</A> Albery WJ. Foulds AW. Hall KJ. Hillman AR. Edgell RG. Orchard AF. Nature  1979,  282:  793 

<A NAME="RT16907SS-3A">3a</A> Nishiwaki E. Nakagawa H. Takasaki M. Matsumoto T. Sakurai H. Shibuya M. Heterocycles  1990,  31:  1763 

<A NAME="RT16907SS-3B">3b</A> Decuyper J. Piette J. Lopez M. Merville MP. Vorst A. Biochem. Pharmacol.  1984,  33:  4025 

<A NAME="RT16907SS-3C">3c</A> Motten AG. Buettner GR. Chignell CF. Photochem. Photobiol.  1985,  42:  9 

<A NAME="RT16907SS-3D">3d</A> Fujita H. Matsuo I. Chem. Biol. Interac.  1988,  66:  27 

<A NAME="RT16907SS-4A">4a</A> Forrest I. Forrest F. Biochim. Biophys. Acta  1958,  29:  441 

<A NAME="RT16907SS-4B">4b</A> Iida Y. Bull. Chem. Soc. Jpn.  1971,  44:  663 

<A NAME="RT16907SS-4C">4c</A> Moutet J.-C. Reverdy G. Nouv. J. Chim.  1983,  7:  105 

For UV/Vis and EPR spectra of 10-methylphenothiazine, see, for example:

<A NAME="RT16907SS-5A">5a</A> Shine HJ. Mach EE. J. Org. Chem.  1965,  30:  2130 

<A NAME="RT16907SS-5B">5b</A> Shine HJ. Thompson DR. Veneziani C. J. Heterocycl. Chem.  1967,  4:  517 

<A NAME="RT16907SS-5C">5c</A> For cyclovoltammetric and spectroscopic data of phenothiazine, see, for example: Tinker LA. Bard AJ. J. Am. Chem. Soc.  1979,  101:  2316 

<A NAME="RT16907SS-5D">5d</A> Padusek B. Kalinowski MK. Electrochim. Acta  1983,  28:  639 

<A NAME="RT16907SS-5E">5e</A> McIntyre R. Gerischer H. Ber. Bunsen Ges. Phys. Chem.  1984,  88:  963 

<A NAME="RT16907SS-6A">6a</A> Duesing R. Tapolsky G. Meyer TJ. J. Am. Chem. Soc.  1990,  112:  5378 

<A NAME="RT16907SS-6B">6b</A> Jones WE. Chen P. Meyer TJ. J. Am. Chem. Soc.  1992,  114:  387 

<A NAME="RT16907SS-6C">6c</A> Brun AM. Harriman A. Heitz V. Sauvage J.-P. J. Am. Chem. Soc.  1991,  113:  8657 

<A NAME="RT16907SS-6D">6d</A> Burrows HD. Kemp TJ. Welburn MJ. J. Chem. Soc., Perkin Trans. 2  1973,  969 

<A NAME="RT16907SS-6E">6e</A> Collin J.-P. Guillerez S. Sauvage J.-P. J. Chem. Soc., Chem. Commun.  1989,  776 

<A NAME="RT16907SS-6F">6f</A> Daub J. Engl R. Kurzawa J. Miller SE. Schneider S. Stockmann A. Wasielewski MR. J. Phys. Chem. A  2001,  105:  5655 

<A NAME="RT16907SS-7A">7a</A> Wheland RC. Gillson JL. J. Am. Chem. Soc.  1976,  98:  3916 

<A NAME="RT16907SS-7B">7b</A> Berges P. Kudnig J. Klar G. Sanchez-Martinez E. Diaz-Calleja R. Synth. Met.  1992,  46:  207 

<A NAME="RT16907SS-7C">7c</A> Knorr A. Daub J. Angew. Chem., Int. Ed. Engl.  1995,  34:  2664 

<A NAME="RT16907SS-7D">7d</A> Spreitzer H. Scholz M. Gescheidt G. Daub J. Liebigs Ann. Chem.  1996,  2069 

<A NAME="RT16907SS-7E">7e</A> Spreitzer H. Daub J. Chem. Eur. J.  1996,  2:  1150 

<A NAME="RT16907SS-8A">8a</A> For applications of AFM and STM in chemistry, see papers in the dedicated issue of Chem. Rev.  1997,  97:  1015-1230  ; issue 4

<A NAME="RT16907SS-8B">8b</A> For applications in molecular electronics, see, for example: Rabe JP. In An Introduction to Molecular Electronics   Petty MC. Bryce MR. Bloor D. Oxford University Press; New York: 1995.  p.261-278  

<A NAME="RT16907SS-8C">8c</A> For nanoscale materials, see papers in the dedicated issue of Acc. Chem. Res.  1999,  32:  387-454  ; issue 5

For conductance of single molecules under STM conditions, see, for example:

<A NAME="RT16907SS-9A">9a</A> Bumm LA. Arnold JJ. Cygan MT. Dunbar TD. Burgin TP. Jones LII. Allara DL. Tour JM. Weiss PS. Science  1996,  271:  1705 

<A NAME="RT16907SS-9B">9b</A> Davis WB. Svec WA. Ratner MA. Wasielewski MR. Nature  1998,  396:  60 

<A NAME="RT16907SS-9C">9c</A> Cygan MT. Dunbar TD. Arnold JJ. Bumm LA. Shedlock NF. Burgin TP. Jones LII. Allara DL. Tour JM. Weiss PS. J. Am. Chem. Soc.  1998,  120:  2721 

<A NAME="RT16907SS-9D">9d</A> Leatherman G. Durantini EN. Gust D. Moore TA. Moore AL. Stone S. Zhou Z. Rez P. Liu YZ. Lindsay SM. J. Phys. Chem. B  1999,  103:  4006 

<A NAME="RT16907SS-10A">10a</A> Müller TJJ. Tetrahedron Lett.  1999,  40:  6563 

<A NAME="RT16907SS-10B">10b</A> Krämer CS. Zeitler K. Müller TJJ. Org. Lett.  2000,  2:  3723 

<A NAME="RT16907SS-10C">10c</A> Krämer CS. Müller TJJ. Eur. J. Org. Chem.  2003,  3534 

<A NAME="RT16907SS-10D">10d</A> Hauck M. Schönhaber J. Zucchero AJ. Hardcastle KI. Müller TJJ. Bunz UHF. J. Org. Chem.  2007,  72:  6714 

<A NAME="RT16907SS-11">11</A> Krämer CS. Zeitler K. Müller TJJ. Tetrahedron Lett.  2001,  42:  8619 

<A NAME="RT16907SS-12A">12a</A> Miyaura N. Suzuki A. Chem. Rev.  1995,  95:  2457 

<A NAME="RT16907SS-12B">12b</A> Suzuki A. In Metal-Catalyzed Cross-Coupling Reactions   Stang PJ. Diederich F. Wiley-VCH; Weinheim: 1998.  p.49-97  

<A NAME="RT16907SS-12C">12c</A> Stanforth SP. Tetrahedron  1998,  54:  263 

<A NAME="RT16907SS-12D">12d</A> Suzuki A. J. Organomet. Chem.  1999,  576:  147 

<A NAME="RT16907SS-13">13</A> For an overview of modern cross-coupling reactions, see: Metal-Catalyzed Cross-Coupling Reactions   de Meijere A. Diederich F. Wiley-VCH; Weinheim: 2004. 2nd ed.; and references cited therein

<A NAME="RT16907SS-14A">14a</A> Murata M. Watanabe S. Masuda Y. J. Org. Chem.  1997,  62:  6458 

<A NAME="RT16907SS-14B">14b</A> Murata M. Oyama T. Watanabe S. Masuda Y. J. Org. Chem.  2000,  65:  164 

<A NAME="RT16907SS-15">15</A> Krämer CS. Zimmermann TJ. Sailer M. Müller TJJ. Synthesis  2002,  1163 

<A NAME="RT16907SS-16A">16a</A> Sailer M. Nonnenmacher M. Oeser T. Müller TJJ. Eur. J. Org. Chem.  2006,  423 

<A NAME="RT16907SS-16B">16b</A> Sailer M. Rominger F. Müller TJJ. J. Organomet. Chem.  2006,  691:  299 

<A NAME="RT16907SS-16C">16c</A> Sailer M. Gropeanu R.-A. Müller TJJ. J. Org. Chem.  2003,  68:  7509 

<A NAME="RT16907SS-17">17</A> Sailer M. Franz AW. Müller TJJ. Chem. Eur. J.  2008,  14:  2602 

<A NAME="RT16907SS-18A">18a</A> Bucci N. Müller TJJ. Tetrahedron Lett.  2006,  47:  8323 

<A NAME="RT16907SS-18B">18b</A> Bucci N. Müller TJJ. Tetrahedron Lett.  2006,  47:  8329 

<A NAME="RT16907SS-19">19</A>

Franz, A. W.; Stoycheva, S.; Himmelhaus, M.; Müller, T. J. J., manuscript in preparation.

<A NAME="RT16907SS-20A">20a</A> Ishiyama T. Murata M. Miyaura N. J. Org. Chem.  1995,  60:  7508 

<A NAME="RT16907SS-20B">20b</A> Ishiyama T. Ishida K. Miyaura N. Tetrahedron  2001,  57:  9813 

<A NAME="RT16907SS-20C">20c</A> Read MW. Escobedo JO. Willis DM. Beck PA. Strongin RM. Org. Lett.  2000,  2:  3201 

<A NAME="RT16907SS-21A">21a</A> Carbonnelle A.-C. Zhu J. Org. Lett.  2000,  2:  3477 

<A NAME="RT16907SS-21B">21b</A> Mizutani T. Wada K. Kitagawa S. J. Am. Chem. Soc.  2001,  123:  6459 

<A NAME="RT16907SS-22">22</A> Becker HGO. Beckert R. Domschke G. Fanghänel E. Habicher WD. Metz P. Pavel D. Schwetlick K. Organikum   Wiley-VCH; Weinheim: 2001.  21st ed.