Ti-Catalyzed Radical Alkylation of Secondary and Tertiary Alkyl Chlorides Using Michael Acceptors
2018-10-10T00:00:00Z (GMT)
by
Alkyl
chlorides are common functional groups in synthetic organic
chemistry. However, the engagement of unactivated alkyl chlorides,
especially tertiary alkyl chlorides, in transition-metal-catalyzed
C–C bond formation remains challenging. Herein, we describe
the development of a TiIII-catalyzed radical addition of
2° and 3° alkyl chlorides to electron-deficient alkenes.
Mechanistic data are consistent with inner-sphere activation of the
C–Cl bond featuring TiIII-mediated Cl atom abstraction.
Evidence suggests that the active TiIII catalyst is generated
from the TiIV precursor in a Lewis-acid-assisted electron
transfer process.
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CC BY-NC 4.0