Cyanide ion promoted addition of acyl phosphonates to ethyl cyanoformate: synthesis of tertiary carbinols via tandem carbon-carbon bond formations.
New cyanation/phosphonate-phosphate rearrangement/C-acylation reactions of cyanophosphate anion with cyanoformate esters are described. Phase-transfer cocatalysts facilitate cyanide-catalyzed reactions between acyl phosphonates and cyanoformates to afford protected tertiary carbinol products in good to excellent yields (74-95%). Ethyl cyanoformate is used as a cyanide source and electrophile. The scope of the reaction was investigated by using a number of benzoyl and acyl phosphonates along with ethyl cyanoformate. Representative chemoselective reduction of the product 5a afforded ethyl 3-amino-2-hydroxy-2-phenylpropanoate (13) in good yield.
Demir
Ayhan S
AS
Department of Chemistry, Middle East Technical University, 06531 Ankara, Turkey. asdemir@metu.edu.tr
Reis
Barbaros
B
Reis
Omer
O
Eymür
Serkan
S
Göllü
Mehmet
M
Tural
Servet
S
Saglam
Gülüzar
G
D003486:Cyanides / Q000737:chemistry*; D004952:Esters / Q000138:chemical synthesis; D005561:Formates / Q000737:chemistry*; D009570:Nitriles / Q000138:chemical synthesis / Q000737:chemistry*; D063065:Organophosphonates / Q000737:chemistry*
D003486:Cyanides; D004952:Esters; D005561:Formates; D009570:Nitriles; D063065:Organophosphonates