Fig. 3. Halogen–sodium exchange between aryl and alkenyl halides and neopentylsodium.

Neopentylsodium prepared in situ from neopentyl chloride (200 mol%) and SD (420 mol%) was reacted with organic halides (1, 0.25 mmol) in hexane (2.0 mL) at 0 °C, followed by addition of R₃SiCl (1.2 equiv), R₂SiCl₂ (2.0 equiv), or D₂O (1.0 mL) as an electrophile. Yields determined by isolation are shown unless otherwise noted. Deuterium content was determined by ¹H NMR. ^aMe₃SiCl (1.2 equiv). ^b(Dodecyl)Me₂SiCl (1.2 equiv). ^cExchange reaction at –40 °C for 10 min. ^dRatio of monosilylated and disilylated products were determined by ¹H NMR. ^eNeopentyl chloride (300 mol%), SD (630 mol%), hexane (2.5 mL), and PhMe₂SiCl (3.0 equiv); after reaction, the concentrated crude mixture was reacted with K₂CO₃ (5.0 equiv) in MeOH (3.0 mL) for 1 h. ^fExchange reaction at –78 °C. ^gTHF (0.80 mL) was used as a co-solvent. ^hNeopentyl chloride (120 mol%) and SD (250 mol%). ⁱExchange reaction for 10 min. ^jNeopentyl chloride (300 mol%), SD (630 mol%), hexane (2.5 mL), and PhMe₂SiCl (3.0 equiv). ^kNeopentyl chloride (340 mol%), SD (710 mol%), hexane (2.5 mL), and R₂SiCl₂ (2.0 equiv). ^l4.0 mmol scale. SD sodium dispersion, ^tBu tert-butyl, Ph phenyl, Me methyl, MeO methoxy.