A Convenient Route to 2-Lithio-1,3-butadiene from Chloroprene via 2-Stannyl-1,3-butadiene

Abstract

A convenient route to 2-lithio-1,3-butadiene from chloroprene via a 2-stannyl-1,3-butadiene is presented, and the regioselecdve additions to a variety of carbonyl groups are demonstrated.

Carbanion generation through tin-lithium exchange of vinyl-, aryl-, and hetarylstannanes

“…2-Lithio-1,3-butadiene was generated from the reaction of 2-tributylstannyl-1,3-butadiene with BuLi in THF (Equation 13). 29 The resulting butadienyl anion, which exists in equilibrium with the allenyl anion, was reacted with various carbonyl compounds to give the corresponding alcohols in good yields. The 1,3-butadienyl product was the predominant product in almost all cases.…”

1,3-Butadienyl-2-magnesium Chloride

“…6,7 The former is a useful precursor for 1,3-Butadienyl-2-lithium. 6 MgCl Mtl MtlCl Mtl = Me 2 SiCl, 44% Mtl = Bu 3 Sn, 89% Mtl = SePh, 70%…”

Unsaturated Nitriles: Optimized Coupling of the Chloroprene Grignard Reagent1 with ω-Bromonitriles

“…In conclusion, the coupling of 2 with ω-bromonitriles affords good yields of unsaturated nitriles that are not directly available by other chloroprene-based coupling procedures …”