tert-Butyldimethylsilyldihalomethyllithium as a dihalomethylene dianion synthon. 1,3-Rearrangement and 1,4-rearrangement of silyl group from carbon to oxide

Article abstract of DOI:10.1016/0040-4020(95)00903-5

One-pot synthesis of R¹CH(OSiMe₂-t-Bu)CX₂CH(OH)R² (X = Cl, Br) by successive addition of two different aldehydes (R¹CHO and R²CHO) has been achieved starting from tert-butyldimethylsilyldihalomethyllithium. Treatment of a THF solution of the title carbanion (X = Cl) with p-MeOC₆H₄CHO or n-BuCHO followed by an addition of HMPA and benzaldehyde gave the corresponding 1,3-diol monosilyl ether in 83% or 45% yield, respectively. The use of oxirane in place of aldehyde as the first electrophile followed by addition of benzaldehyde provided 1,4-diol monosilyl ether.