Abstract

Asymmetric alkynylation of seven-membered cyclic imine dibenzo[b,f][1,4]oxazepines is successfully achieved by combining chiral phosphoric acid and Ag(I) catalysts. Various arylacetylenes, conjugated enynes, and terminal 1,3-diynes are good substrates for this reaction, and aliphatic hexyne is also a suitable donor at elevated temperature. Optimization of this approach has provided a facile method to synthesize optically active 11-substituted-10,11-dihydrodibenzo[b,f][1,4]oxazepine derivatives containing a carbon–carbon triple bond with 63–99% ee. Subsequent transformations of the carbon–carbon triple bond for the heterocyclic products have been disclosed.

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