Palladium-catalyzed Formation of Heterocycles by Coupling of Dibromoarenes and Sulfoximines

Abstract

The palladium-catalyzed reaction between dibromo­arenes and sulfoximines affords 6 to 8-membered heterocycles in excellent yields. The reaction sequence involves an intermolecular N-arylation followed by an intramolecular ring closure.

catalysis - cross-coupling - heterocycles - palladium - sulfoximines

References

Reviews:

<A NAME="RG06302ST-1A">1a</A> Johnson CR. Aldrichimica Acta  1985,  18:  3 

<A NAME="RG06302ST-1B">1b</A> Johnson CR. Acc. Chem. Res.  1973,  6:  341 

<A NAME="RG06302ST-1C">1c</A> Pyne SG. Sulfur Rep.  1992,  12:  57 

<A NAME="RG06302ST-1D">1d</A> Reggelin M. Zur C. Synthesis  2000,  1 

Selected examples:

<A NAME="RG06302ST-2A">2a</A> Pyne SG. Dong Z. Skelton BW. White AW. J. Org. Chem.  1997,  62:  2337 

<A NAME="RG06302ST-2B">2b</A> Reggelin M. Heinrich T. Angew. Chem. Int. Ed.  1998,  37:  2883 ; Angew. Chem. 1998, 110, 3005

<A NAME="RG06302ST-2C">2c</A> Bosshammer S. Gais H.-J. Synthesis  1998,  919 

<A NAME="RG06302ST-2D">2d</A> Paquette LA. Gao Z. Ni Z. Smith GF. J. Am. Chem. Soc.  1998,  120:  2543 

<A NAME="RG06302ST-2E">2e</A> Harmata M. Kahraman M. Jones DE. Pavri N. Weatherwax SE. Tetrahedron  1998,  54:  9995 

<A NAME="RG06302ST-3A">3a</A> Bolm C. Felder M. Müller J. Synlett  1992,  439 

<A NAME="RG06302ST-3B">3b</A> Bolm C. Felder M. Tetrahedron Lett.  1993,  34:  6041 

<A NAME="RG06302ST-3C">3c</A> Bolm C. Müller J. Schlingloff G. Zehnder M. Neuburger M. J. Chem. Soc., Chem. Commun.  1993,  182 

<A NAME="RG06302ST-3D">3d</A> Bolm C. Seger A. Felder M. Tetrahedron Lett.  1993,  34:  8079 

<A NAME="RG06302ST-3E">3e</A> Bolm C. Felder M. Synlett  1994,  655 

<A NAME="RG06302ST-3F">3f</A> Bolm C. Müller P. Tetrahedron Lett.  1995,  36:  1625 

<A NAME="RG06302ST-3G">3g</A> Bolm C. Müller P. Acta Chem. Scand.  1996,  50:  305 

<A NAME="RG06302ST-4A">4a</A> Bolm C. Kahmann JD. Moll G. Tetrahedron Lett.  1997,  38:  1169 

<A NAME="RG06302ST-4B">4b</A> Bolm C. Moll G. Kahmann JD. Chem.-Eur. J.  2001,  7:  1118 

<A NAME="RG06302ST-4C">4c</A> Bolm C. Müller D. Hackenberger CHP. Org. Lett.  2002,  4:  893 

<A NAME="RG06302ST-5A">5a</A> Bolm C. Hildebrand JP. Tetrahedron Lett.  1998,  39:  5731 

<A NAME="RG06302ST-5B">5b</A> Bolm C. Hildebrand JP. J. Org. Chem.  2000,  65:  169 

<A NAME="RG06302ST-5C">5c</A> Bolm C. Hildebrand JP. Rudolph J. Synthesis  2000,  911 

<A NAME="RG06302ST-6">6</A> Bolm C. SimiÊ O. J. Am. Chem. Soc.  2001,  123:  3830 

<A NAME="RG06302ST-7A">7a</A> Bolm C. SimiÊ O. Martin M. Synlett  2001,  1878 

<A NAME="RG06302ST-7B">7b</A> For the use of a related compound, see also: Harmata M. Ghosh SK. Org. Lett.  2001,  3:  3321 

<A NAME="RG06302ST-8">8</A>

Bolm, C.; Martin, M.; SimiÊ, O.; Verrucci, M., submitted for publication.

<A NAME="RG06302ST-9">9</A>

In a typical experiment [Pd₂(dba)₃] (36.0 mg, 0.04 mmol) and rac-BINAP (50.0 mg, 0.08 mmol) were dissolved in 20 mL of toluene under an argon atmosphere and refluxed for 10 min. After cooling of the resulting red solution to room temperature, NaO-tBu (384 mg, 4.06 mmol), sulfoximine 1a (776.0 mg, 5.0 mmol), and 2,2′-dibromobiphenyl (312.0 mg, 1.0 mmol) were added and stirring was continued under reflux for an additional 20 h. The suspension was diluted with diethyl ether at room temperature and filtered through a plug of celite. After removing the volatile compounds, the product was directly purified by column chromatography (silica, pentane-ethyl acetate 3:1, R_f = 0.49) furnishing 7a (300 mg, 0.98 mmol, 98%) as a colorless solid, which could be crystallized in ethyl acetate. Mp: 229 °C; [α]_D = +62.6
(c = 1, CHCl₃). ¹H NMR (400 MHz, CDCl₃): δ 4.27 (d, J = 15 Hz, 1 H, CH _a H_b), 4.44 (d, J = 15 Hz, 1 H, CH_a H _b ), 6.68 (d, J = 8 Hz, 1 H, CH _aryl ), 7.15-7.65 (m, 13 H, CH _aryl ).
¹³C NMR (100 MHz, CDCl₃): δ 58.5, 123.3, 127.0, 127.8, 128.4, 128.7, 129.1, 129.7, 129.8, 130.1, 133.5, 135.7, 140.0, 142.3. MS: m/z (%) 305 (M⁺, 24), 180(100), 152(28). IR (KBr): 685, 724, 768, 782, 810, 872, 995, 1018, 1026, 1109, 1144, 1176, 1206, 1240, 1258, 1281, 1434, 1445, 1475, 1592, 2906, 2972, 3054, 3099 cm^-1. Anal. calcd for C₁₉H₁₅NOS: C, 74.73; H, 4.95; N, 4.59; found: C, 74.76;
H, 5.06; N, 4.54.

<A NAME="RG06302ST-10">10</A>

Unless indicated otherwise, [Pd₂(dba)₃] was used as the catalyst.

<A NAME="RG06302ST-11">11</A> Lee S. Hartwig JF. J. Org. Chem.  2001,  66:  3402 

For a selection of recent Pd-catalyzed arylations of CH-acidic substrates, see:

<A NAME="RG06302ST-12A">12a</A> Culkin DA. Hartwig JF. J. Am. Chem. Soc.  2001,  123:  5816 

<A NAME="RG06302ST-12B">12b</A> Lee S. Beare NA. Hartwig JF. J. Am. Chem. Soc.  2001,  123:  8410 

<A NAME="RG06302ST-12C">12c</A> Stauffer SR. Beare NA. Stambuli JP. Hartwig JF. J. Am. Chem. Soc.  2001,  123:  4641 

<A NAME="RG06302ST-12D">12d</A> Gaertzen O. Buchwald SL. J. Org. Chem.  2002,  67:  465 

<A NAME="RG06302ST-12E">12e</A> Moradi WA. Buchwald SL. J. Am. Chem. Soc.  2001,  123:  7996 

<A NAME="RG06302ST-12F">12f</A> Vogl EM. Buchwald SL. J. Org. Chem.  2002,  67:  106 

<A NAME="RG06302ST-12G">12g</A> Hamada T. Chieffi A. Åhman J. Buchwald SL. J. Am. Chem. Soc.  2002,  124:  1261 

<A NAME="RG06302ST-12H">12h</A> Honda T. Namiki H. Satoh F. Org. Lett.  2001,  3:  631 

<A NAME="RG06302ST-13">13</A>

Isolated 1-bromo-2-N-[S-methyl-S-phenylsulfonimidoyl]-benzene also did not cyclize when subjected to the typical coupling conditions described in ref. [9]

<A NAME="RG06302ST-14">14</A> Harmata M. Pavri N. Angew. Chem. Int. Ed.  1999,  38:  2419