An efficient palladium-catalyzed 2-fluoroallylation of P(O)H compounds with gem-difluorocyclopropanes is presented. The reaction provides a variety of 2-fluoroallylic phosphorus compounds in good yields with high Z selectivity through the sequential C−C bond activation, C−F bond cleavage, and C−P coupling process. Various H-phosphonates, H-phosphinates, and secondary phosphine oxides are all tolerated. In addition, the gram-scale synthesis and the late-stage modification of complex bioactive molecules show practical utilities of the transformation.
We
report herein a concise method for the construction of phosphinonyl-azaindoline
and -azaoxindole derivatives via a palladium-catalyzed cascade cyclization
with P(O)H compounds. Various H-phosphonates, H-phosphinates, and aromatic secondary phosphine oxides
are all tolerated under the reaction conditions. Furthermore, the
phosphinonyl-azaindoline isomer families such as 7-, 5-, and 4-azaindolines
could be synthesized in moderate to good yields.
A highly regioselective and stereoselective cascade reduction cyclization of δ-ketoamide is realized under LiAlH4 assisted conditions, providing an atom-economical and straightforward approach to access oxa-bridged benzazepines in moderate to good...
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