Highly efficient asymmetric synthesis of vinylic amino alcohols by Zn-promoted benzoyloxyallylation of chiral N-tert-butanesulfinyl imines: facile and rapid access to (-)-cytoxazone.
An efficient and convenient alpha-hydroxyallylation approach for the asymmetric synthesis of a variety of beta-amino-alpha-vinyl alcohols has been successfully developed. A wide range of vinylic amino alcohol derivatives could be obtained in very good yields and with excellent diastereomeric ratios of up to 99:1 in favor of anti isomers by highly diastereoselective Zn-promoted benzoyloxyallylation of chiral N-tert-butanesulfinyl imines with 3-bromopropenyl benzoate at room temperature. In particular, excellent enantioinduction of the two new stereogenic centers was observed, with up to 98% ee. The method provides a new route for the direct alpha-hydroxyallylation of imines in a highly stereoselective manner. Moreover, the synthetic value of the method has also been demonstrated by the most concise and straightforward synthesis of (-)-cytoxazone yet reported.
Liu
Min
M
Key Laboratory of Synthetic Chemistry of Natural Substances, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, 345 Lingling Road, Shanghai 200032, China.
Sun
Xing-Wen
XW
Xu
Ming-Hua
MH
Lin
Guo-Qiang
GQ
D000605:Amino Alcohols / Q000138:chemical synthesis* / Q000737:chemistry; D002384:Catalysis; D003432:Cross-Linking Reagents; D007097:Imines / Q000737:chemistry*; D015394:Molecular Structure; D010080:Oxazoles / Q000737:chemistry*; D013237:Stereoisomerism; D013438:Sulfhydryl Compounds / Q000737:chemistry*; D014753:Vinyl Compounds / Q000138:chemical synthesis* / Q000737:chemistry
D000605:Amino Alcohols; D003432:Cross-Linking Reagents; D007097:Imines; D010080:Oxazoles; D013438:Sulfhydryl Compounds; D014753:Vinyl Compounds; C117832:cytoxazone