Tandem carbon-carbon bond constructions via catalyzed cyanation/Brook rearrangement/C-acylation reactions of acylsilanes.
[reaction: see text] A tandem nucleophile-catalyzed cyanation/Brook rearrangement/C-acylation has been developed. Phase transfer cocatalysts facilitate cyanide-catalyzed reactions between acylsilanes and cyanoformates to afford protected tertiary carbinol products. A catalytic cycle is proposed involving cyanation of an acylsilane, [1,2]-Brook rearrangement, and C-acylation of the derived carbanion by a cyanoformate ester. The reaction offers an efficient method for the preparation of functionalized, unsymmetrical malonic acid derivatives.
Linghu
Xin
X
Department of Chemistry, University of North Carolina at Chapel Hill, Chapel Hill, North Carolina 27599-3290, USA.
Nicewicz
David A
DA
Johnson
Jeffrey S
JS