||Contiguous radical pivaloyloxymethylation–directed C(sp3)–H iodination of N-tosyl cycloalkanecarbaldimine
Fujii, Shintaro ,
Nakano, Mayu ,
Yamaoka, Yousuke ,
Takasu, Kiyosei ,
Yamada, Ken-ichiTomioka, Kiyoshi
3089 , 2015-06 , Elsevier Ltd.
Available online 27 November 2014
A reaction of N-tosyl cycloalkanecarbaldimines with iodomethyl pivalate was initiated by triethylborane to give pivaloyloxymethylated products bearing 3-iodocycloalkyl groups. Radical addition of pivaloyloxymethyl to imines generates aminyl radicals, which then regioselectively cleave Csingle bondH bonds at the 3-position of the cycloalkane moieties. The resulting carbon-centered radicals are trapped with iodine. DFT calculations rationalized stereo- and regioselectivity.