Synthesis of ortho-haloaminoarenes by aryne insertion of nitrogen-halide bonds.
Journal Article (Journal Article)
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.
Full Text
Duke Authors
Cited Authors
- Hendrick, CE; Wang, Q
Published Date
- January 2015
Published In
Volume / Issue
- 80 / 2
Start / End Page
- 1059 - 1069
PubMed ID
- 25495648
Electronic International Standard Serial Number (EISSN)
- 1520-6904
International Standard Serial Number (ISSN)
- 0022-3263
Digital Object Identifier (DOI)
- 10.1021/jo502541t
Language
- eng