Dichloromethane → 2-(1-Chloro-3-methylbutyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane

Reaction equation

C([Li])[CH2:2][CH2:3][CH3:4].[CH3:6][C:7]1([CH3:18])[C:11]([CH3:13])([CH3:12])[O:10][B:9](CC(C)C)[O:8]1.[CH2:19](COC)OC.[CH2:25]([Cl:27])Cl>>[Cl:27][CH:25]([B:9]1[O:10][C:11]([CH3:12])([CH3:13])[C:7]([CH3:18])([CH3:6])[O:8]1)[CH2:19][CH:3]([CH3:2])[CH3:4]

Participants

Reactant 4

HCID 6344Dichloromethane

HCID 80711,2-Dimethoxyethane

HCID 134912534,4,5,5-Tetramethyl-2-(2-methylpropyl)-1,3,2-dioxaborolane

HCID 178418339Butyllithium

Product 1

HCID 134912542-(1-Chloro-3-methylbutyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolaneYield 39.46%

Procedure

134 mL n-butyllithium (1.6 M, 0.221 mol) were added to 31.08 mL (22.43 g, 0.221 mol) ice-cold diisopropylamine containing 3 mL tetrahydrofuran. The resulting thick liquid was added to a solution of 33.98 g (0.185 mol) 4,4,5,5-tetramethyl-2-(2-methylpropyl)-1,3,2-dioxaborolane (2) in 165 mL glyme containing 17.72 mL (23.5 g, 0.277 mol) methylene chloride at -72°. When this addition was complete, the reaction mixture was stirred for 2 hours, diluted with 165 mL methylene chloride, and a white precipitate removed by filtration. The residue was washed twice with 25 mL portions of methylene chloride. The filtrates were combined, concentrated under reduced pressure, and then distilled from a 12" spinning band column, providing 16.96 g (0.087 mol, 39.46%) of an oil, bp 90°-93°/2.0 mm; 1H NMR (90 MHz, CDCl3): δ0.90 (d, d, J=6, 3 Hz, 6), 1.3 (s, 12), 1.73 (m, 3), 3.45 (d, d, J=6 Hz, 1); Anal. Calcd. for C11H22O2ClB: C, 56.81; H, 9.53; Cl, 15.24; B, 4.65; Found: C, 56.81; H, 9.46; Cl, 15.37; B, 4.53.