Programmed synthesis of a contiguous stereotriad motif by triple stereospecific reagent-controlled homologation.
All distinct diastereoisomers of a contiguous stereotriad motif were separately targeted by a triple chain extension of B-phenethyl boronic esters using four unique presentation sequences of enantiomorphs of 1-[(2)H]-1-chloro-2-(1,3-dioxolan-2-yl)ethyllithium. The (R)- or (S)-configured chloroalkyllithium reagents were generated by sulfoxide-lithium exchange from the appropriate scalemic p-tolyl chloroalkyl sulfoxides using phenyllithium (THF, -78 °C). Stereotriad synthesis was accomplished in a single reaction vessel [7-19% yield, typical dr ≥ 74 (target):26 (∑ all other isomers)] and implemented by a simple algorithm consisting of reagent charging and temperature cycling events.
Department of Chemistry, Oregon State University, Corvallis, Oregon 97331-4003, USA.
Xun
X
Sun
Paul R
PR
Blakemore