Diastereoselective [2,3]-sigmatropic rearrangements of lithium N-benzyl-O-allylhydroxylamides bearing a stereogenic centre adjacent to the migration terminus

Journal article

The diastereoselective [2,3]-sigmatropic rearrangements of lithium N-benzyl-O-allylhydroxylamides bearing a stereogenic centre adjacent to the migration terminus are examined. (E)-N-Benzyl-O-(4-phenylpent-2-enyl)-hydroxylamine rearranges in 30% de to afford syn-(3RS,4RS)-3-(N-benzyl-N-hydroxy)-4-phenylpent-1-ene as the major diastereoisomer, consistent with the rearrangement proceeding under moderate steric control. Rearrangements of both lithium (E)- and (Z)-N-benzyl-O-(4-methoxy-4-phenylbut-2-enyl)hydroxylamides furnish syn-(1RS,2RS)-1-phenyl-1-methoxy-3-(N-benzylamino)but-3-ene in≥90% and 88% de respectively, consistent with these rearrangements proceeding under chelation control.

Authors: Bull, S; Davies, S; Domingez, S; Jones, S; Price, A

• Publication status: Published
• Journal: JOURNAL OF THE CHEMICAL SOCIETY-PERKIN TRANSACTIONS 1
• Issue: 19
• Pages: 2141-2150
• Publication date: 2002-01-01
• DOI: 10.1039/b207069n
• EISSN: 1364-5463
• ISSN: 1472-7781
• Language: English