1-bromo-4-methylsulfanylbenzene

Conditions: temp:0.00; pressure:0.00; stir:

Conditions: temp:0.00; pressure:0.00; stir:

Conditions: temp:0.00; pressure:0.00; stir:

Conditions: temp:0.00; pressure:0.00; stir:

Conditions: temp:55.01; pressure:0.00; stir:

Procedure: dtbpy: A mixture of ortho- and meta-borylated products (125 mg, 76% yield, ortho/meta + para = 3.0); yellow oil;

Conditions: temp:55.01; pressure:0.00; stir:

Procedure: Ligand 3f: A mixture of ortho- and meta-borylated products (139 mg, 85% yield, ortho/meta + para = 6.6); ortho-borylated product 4f was obtained by further purification by GPC (101 mg, 62% yield), yellow solid (mp. 88-90 oC)

Conditions: temp:0.00; pressure:0.00; stir:

Conditions: temp:0.00; pressure:0.00; stir:

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: 1-(5-(4-(Methylthio)phenyl)thien-2-yl)ethanone is prepared from 5-acetyl-2-thiopheneboronic acid and 1-bromo-4-(methylthio)benzene according to general procedure A.

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: Following the procedure describe in Method 3, but substituting4-methylthiostyrene and 1-bromo-3-fluorobenzene for 4-fluorostyrene and 4-bromothioanisole, the title product was obtained as an off-white solid.

Conditions: temp:120.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: In a 4 mL vial charged with a stir bar, N-1,3-thiazol-2-ylpyrrolidine-1-carboxamide (53 mg, 0.27 mmol, Example 32A) was added, followed by copper(I) trifluoromethanesulfonate benzene complex (27 mg, 0.05 mmol), 5-chloro-1,10-phenanthroline (23 mg, 0.11 mmol) and cesium carbonate (97 mg, 0.3 mmol). A loose cap with a septum was placed on the vial, and then the vial was placed under vacuum in a vacuum oven for 30 minutes. The mixture was purged with nitrogen gas a couple of times. Then (4-bromophenyl)(methyl)sulfane (61 mg, 0.3 mmol) dissolved in 1-methyl-2-pyrrolidinone (1.0 mL) was added to the solid mixture. The vial was capped and placed on a heater/stirrer and heated to 120° C. overnight. Then a 1 mL solution of concentrated ammonium hydroxide/water (1:2) was added. The reaction was filtered and concentrated to dryness. The residue was purified by reverse phase HPLC (C8, gradient 10-100% acetonitrile/water/0.1% trifluoroacetic acid). In a 4 mL vial charged with a stir bar A loose cap with a septum The mixture was purged with nitrogen gas a couple of times was added to the solid mixture The vial was capped placed on a heater/stirrer The reaction was filtered concentrated to dryness The residue was purified by reverse phase HPLC (C8, gradient 10-100% acetonitrile/water/0.1% trifluoroacetic acid)

Conditions: temp:120.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: To a 4 mL vial equipped with a septum cap and stir bar was added N-(5-methyl-1,3-thiazol-2-yl)pyrrolidine-1-carboxamide (50 mg, 0.24 mmol), copper(I) trifluoromethanesulfonate benzene complex (23.8 mg, 0.05 mmol), 5-chloro-1,10-phenanthroline (20.3 mg, 0.09 mmol) and cesium carbonate (84.8 mg, 0.26 mmol). The mixture was placed under a nitrogen atmosphere. (4-Bromophenyl)(methyl)sulfane (0.28 mmol) in 1-methyl-2-pyrrolidinone (1.0 mL) was added to the mixture. The reaction mixture was heated at 120° C. for overnight. A solution of concentrated ammonium hydroxide/water (1:2, 1 mL) was added and the mixture was filtered and solvent removed under reduced pressure. The residue was purified by reverse phase HPLC (C8, gradient 10-100% acetonitrile/water/0.1% trifluoroacetic acid). To a 4 mL vial equipped with a septum cap the mixture was filtered solvent removed under reduced pressure The residue was purified by reverse phase HPLC (C8, gradient 10-100% acetonitrile/water/0.1% trifluoroacetic acid)