cs9b03570_si_001.pdf (20.33 MB)
Photocatalytic Radical Aroylation of Unactivated Alkenes: Pathway to β‑Functionalized 1,4‑, 1,6‑, and 1,7-Diketones
journal contribution
posted on 2019-10-17, 13:45 authored by Satavisha Sarkar, Arghya Banerjee, Wang Yao, Eric V. Patterson, Ming-Yu NgaiWe report the development
of a photocatalytic strategy for the
synthesis of β-functionalized unsymmetrical 1,4-, 1,6-, and
1,7-diketones from aroyl chlorides and unactivated alkenes at room
temperature. The mild reaction conditions not only tolerate a wide
range of functional groups and structural moieties, but also enable
migration of a variety of distal groups including (hetero)arenes,
nitrile, aldehyde, oxime derivative, and alkene. The efficiency of
chirality transfer, factors that control the distal-group migration,
and synthesis of carbocycles and heterocycles from the diketones are
also described. Mechanistic studies suggest a reaction pathway involving
a photocatalytic radical aroylation of unactivated alkenes followed
by a distal-group migration, oxidation, and deprotonation to afford
the desired diketones.