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Representative Procedure, Synthesis of Trimethyl[5-(4,4,5,5- tetramethyl-1,3,2-dioxaborolan-2-yl)thiophen-2-yl]silane (3b; Table 1, Entry 2) In a flame-dried Schlenk flask under N2 atmosphere n-BuLi (2.5 M in n-hexane, 0.83 mL, 2.00 mmol) and TMEDA (0.3 mL, 2.0 mmol) were dissolved in anhyd THF (30 mL) at -78°C. 2,5-Dibromothiophene (1a, 242 mg, 1.00 mmol) was added slowly to the solution, and the mixture was stirred for 30 min. Then, TMSCl (2a, 0.11 g, 1.00 mmol) in anhyd THF (10 mL) was added dropwise to the stirred solution over a period of 3 h. The reaction mixture was stirred for another 30 min and B(OMe)3 (2c, 208 mg, 1.00 mmol) was added. After stirring for 40 min pinacol (130 mg, 1.10 mmol) in anhyd THF (5 mL) was added to the mixture. The solution was allowed to warm to r.t, a few drops of AcOH were added, and the solution was stirred for 14 h. After aqueous workup and extraction with Et2O the com
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Interestingly, the expected byproducts, i.e. symmetrical disubstitution with the first electrophile and monosubstitution with the first electrophile followed by proton quenching are only found in minor quantities and were identified by GC-MS analysis in the crude ethereal extract during workup
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Interestingly, the expected byproducts, i.e. symmetrical disubstitution with the first electrophile and monosubstitution with the first electrophile followed by proton quenching are only found in minor quantities and were identified by GC-MS analysis in the crude ethereal extract during workup.
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(a) Mitsumori, T.; Inoue, K.; Koga, N.; Iwamura, H. J. Am. Chem. Soc. 1995, 117, 2467.
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For recent reviews, see for example: (a) Knochel, P.; Calaza, M. I.; Hupe, E.; Negishi, E.-I.; Liu, F. In Metal-Catalyzed Cross-Coupling Reactions; de Meijere, A.; Diederich, F., Eds.; Wiley-VCH: Weinheim, 2004, 619-670.
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