Stereoselective synthesis of delta-lactones from 5-oxoalkanals via one-pot sequential acetalization, Tishchenko reaction, and lactonization by cooperative catalysis of samarium Ion and mercaptan.
By the synergistic catalysis of samarium ion and mercaptan, a series of 5-oxoalkanals was converted to (substituted) delta-lactones in efficient and stereoselective manners. This one-pot procedure comprises a sequence of acetalization, Tishchenko reaction and lactonization. The deliberative use of mercaptan, by comparison with alcohol, is advantageous to facilitate the catalytic cycle. The reaction mechanism and stereochemistry are proposed and supported by some experimental evidence. Such samarium ion/mercaptan cocatalyzed reactions show the feature of remote control, which is applicable to the asymmetric synthesis of optically active delta-lactones. This study also demonstrates the synthesis of two insect pheromones, (2S,5R)-2-methylhexanolide and (R)-hexadecanolide, as examples of a new protocol for asymmetric reduction of long-chain aliphatic ketones.
Hsu
J L
JL
Department of Chemistry, National Taiwan University, Taipei, Taiwan 106, Republic of China.
Fang
J M
JM
D000107:Acetylation; D002384:Catalysis; D004809:Ephedrine / Q000031:analogs & derivatives / Q000138:chemical synthesis; D007202:Indicators and Reagents; D007477:Ions; D007783:Lactones / Q000138:chemical synthesis*; D012493:Samarium / Q000737:chemistry*; D012724:Sex Attractants / Q000138:chemical synthesis*; D013237:Stereoisomerism; D013438:Sulfhydryl Compounds / Q000138:chemical synthesis / Q000737:chemistry*
D007202:Indicators and Reagents; D007477:Ions; D007783:Lactones; D012724:Sex Attractants; D013438:Sulfhydryl Compounds; D012493:Samarium; D004809:Ephedrine