- Synthesis of ortho -haloaminoarenes by aryne insertion of nitrogen-halide Bonds
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A rapid and general access to ortho-haloaminoarenes has been developed by aryne insertion into N-chloramine, N-bromoamine, and N-iodoamine bonds via two complementary protocols harnessing fluoride-promoted 1,2-elimination of ortho-trimethylsilyl aryltriflates. Typically, electron-deficient N-chloramines effectively react with aryne intermediates generated at elevated temperature with CsF, while less stable N-haloamines are found more efficient under milder, TBAF-mediated aryne formation at room temperature. Both protocols demonstrate a good level of regioselectivity and functional group tolerance. Efforts to elucidate the mechanism of N-X insertion are also discussed. The practical value of this transformation is highlighted by rapid synthesis of novel analogues of the antipsychotic cariprazine.
- Hendrick, Charles E.,Wang, Qiu
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p. 1059 - 1069
(2015/01/30)
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- Insertion of arynes into N-halo bonds: A direct approach to O -haloaminoarenes
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A new approach to access o-haloaminoarenes has been achieved by insertion of arynes into a nitrogen-halide bond (N-X). This transition-metal-free transformation displays a broad substrate scope of arynes, good compatibility with functional groups, and high regioselectivity. Representative transformations of the o-haloaminoarenes are described to highlight their utility for rapid access to diversely functionalized aminoarene derivatives.
- Hendrick, Charles E.,McDonald, Stacey L.,Wang, Qiu
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p. 3444 - 3447
(2013/07/26)
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