Synthesis of carbocyclic hydantocidins via regioselective and diastereoselective phosphine-catalyzed [3 + 2]-cycloadditions to 5-methylenehydantoins.
The phosphine-catalyzed [3 + 2]-cycloaddition of 5-methylenehydantoins 4 with the ylides 5, derived from addition of tributylphosphine to the 2-butynoic acid derivatives, 6a-d, gives spiro-heterocyclic products. The camphor sultam derivative 6b gives optically active products. Noteable was that the ylides derived from ethyl 2-butynoate and the 3-(2-butynoyl)-1,3-oxazolidin-2-one derivatives 6c and 6d gave spiro-heterocyclic products with reverse regioselectivities. The N,N-dibenzylprotected cycloadduct has been converted to carbocyclic hydantocidin and 6,7-diepi-carbocyclic hydantocidin.
Pham
Tien Q
TQ
Department of Chemistry, University of Wollongong, Wollongong, New South Wales, 2522, Australia.
Pyne
Stephen G
SG
Skelton
Brian W
BW
White
Allan H
AH
D001685:Biological Factors / Q000138:chemical synthesis / Q000737:chemistry; D002087:Butyrates / Q000737:chemistry; D002244:Carbon / Q000737:chemistry*; D002384:Catalysis; D003500:Cyclization; D006827:Hydantoins / Q000138:chemical synthesis* / Q000737:chemistry*; D008745:Methylation; D015394:Molecular Structure; D010720:Phosphines / Q000737:chemistry*; D013237:Stereoisomerism
D001685:Biological Factors; D002087:Butyrates; D006827:Hydantoins; D010720:Phosphines; C495862:ethyl 2-butynoate; C043255:tri-n-butylphosphine; C068815:hydantocidin; D002244:Carbon; C044646:phosphine