Raney-Co mediated reductive cyclization of an alpha,beta-unsaturated nitrile.
An expedient, five step synthesis of caprolactam 1 is reported starting from natural L-homoserine. The key step is a chemoselective reductive cyclization of alpha,beta-unsaturated nitrile 10 mediated by Raney-Co type metals. This hydrogenation is extensively investigated in order to account for the observed product distribution and yields.
Janey
Jacob M
JM
Department of Process Research, Merck Research Laboratories, Merck and Co., Inc., Rahway, New Jersey 07065, USA. jacob_janey@merck.com
Orella
Charles J
CJ
Njolito
Eugenia
E
Baxter
Jenny M
JM
Rosen
Jonathan D
JD
Palucki
Michael
M
Sidler
Rick R
RR
Li
Wenjie
W
Kowal
Jason J
JJ
Davies
Ian W
IW
D000447:Aldehydes / Q000138:chemical synthesis / Q000737:chemistry; D002209:Caprolactam / Q000737:chemistry; D003035:Cobalt / Q000737:chemistry*; D003500:Cyclization; D006714:Homoserine / Q000138:chemical synthesis / Q000737:chemistry; D007536:Isomerism; D008715:Methionine / Q000737:chemistry; D015394:Molecular Structure; D009570:Nitriles / Q000737:chemistry*; D010084:Oxidation-Reduction; D013696:Temperature
D000447:Aldehydes; D009570:Nitriles; D003035:Cobalt; D002209:Caprolactam; D006714:Homoserine; D008715:Methionine