title: Asymmetric total synthesis of (+)-inthomycin C via O-directed free radical alkyne hydrostannation with Ph3SnH and catalytic Et3B: reinstatement of the Zeeck-Taylor (3R)-structure for (+)-inthomycin C.
abstract: A new pathway to (+)-inthomycin C is reported that exploits an O-directed free radical hydrostannation reaction on (-)-12 and a Stille cross-coupling as key steps. Significantly, the latter process was effected on 19 where a gauche-pentane repulsive interaction could interfere. Our stereochemical studies on the alkynol (-)-12 and the enyne (+)-7 confirm that Ryu and Hatakeyama's (3S)-stereochemical revision of (+)-inthomycin C is invalid and that Zeeck and Taylor's original (3R)-stereostructure for (+)-inthomycin C is correct.
authors: The School of Chemistry and Chemical Engineering and the Centre for Cancer Research and Cell Biology (CCRCB), the Queen's University Belfast , Stranmillis Road, Belfast BT9 5AG, Northern Ireland, United Kingdom.
authors: Karl J
authors: KJ
authors: Hale
authors: Milosz
authors: M
authors: Grabski
authors: Soraya
authors: S
authors: Manaviazar
authors: Maciej
authors: M
authors: Maczka
mesh_terms: D000480:Alkynes / Q000737:chemistry*; D002384:Catalysis; D005609:Free Radicals; D015394:Molecular Structure; D010080:Oxazoles / Q000138:chemical synthesis* / Q000737:chemistry; D013237:Stereoisomerism
chemical_list: D000480:Alkynes; D005609:Free Radicals; D010080:Oxazoles; C554877:inthomycin C