Asymmetric total syntheses of (+)-3-(z)-laureatin and (+)-3-(z)-isolaureatin by "lone pair-lone pair interaction-controlled" isomerization.
The first asymmetric total syntheses of the dihalogenated medium-sized dioxabicyclic marine natural products (+)-3-(Z)-isolaureatin (1) and (+)-3-(Z)-laureatin (2) have been accomplished. Notable features of the highly stereo-, regio-, and chemoselective syntheses of these alpha,alpha'-trans-oxocene natural products include an intramolecular amide enolate alkylation to construct the alpha,alpha'-cis-oxocene, novel "lone pair-lone pair interaction-controlled" epimerizations to the alpha,alpha'-trans-oxocenes, various strategies for stereoselective introduction of halogen atoms, and novel olefin cross-metatheses for construction of the (Z)-enyne systems.
Kim
Hyoungsu
H
Research Institute of Pharmaceutical Sciences, College of Pharmacy, Seoul National University, San 56-1, Shinrim-Dong, Kwanak-Ku, Seoul 151-742, Korea.
Lee
Hyunjoo
H
Lee
Dongjoo
D
Kim
Sanghee
S
Kim
Deukjoon
D
D004988:Ethers, Cyclic / Q000138:chemical synthesis* / Q000737:chemistry; D008968:Molecular Conformation; D009942:Organometallic Compounds / Q000737:chemistry; D035964:Oxocins / Q000138:chemical synthesis* / Q000737:chemistry; D013237:Stereoisomerism
D004988:Ethers, Cyclic; D009942:Organometallic Compounds; D035964:Oxocins; C017458:laureatin; C017441:isolaureatin